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IUPAC's 1996 Recommendations on Nomenclature of INTERNATIONAL UNION OF PURE AND APPLIED and INTERNATIONAL UNION OF AND MOLECULAR BIOLOGY

JOINT COMMISSION ON BIOCHEMICAL NOMENCLATURE"

NOMENCLATURE OF CARBOHYDRATES (Recommendations 1996) Preparedfor publication by ALAN D. McNAUGHT

The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 4WF. UK

"Members of the Commission (JCBN) at various times during the work on this document (1983-1996) were as follows;

Chnirmen: H.B.F. Oilton (UK), J.F.G. Vliegenthart (Netherlands), A. Comish-Bowden (France); Sure· lariu: A. Cornish-Bowden (France), M.A. Chester (Sweden), AJ. Barrett (UK), J .C. Rigg (Netherlands); Membus: J.R. Bull (RSA), R. Cammack (UK), D. Coucouvanis (USA), D. Horton (USA). M.A.C. Kaplan (Brazil), P. Karlson (Germany), C. Liebecq (Belgium). K.L. Loening (USA), G.P. Moss (UK). J. Reedijk (Netherlands), K.F. Tipton (Ireland), S. Velick (USA). P. Venetianer (Hungary).

Additional contributors to the formulation of these recommendations:

Expert Panel: D. Horton (USA)(Convener), O. Achmatowicz (), L. Anderson (USA), S.J. Angyal (Australia), R. Gigg (UK), B. Lindberg (Sweden). DJ. Manners (UK), H. Paulsen (Germany), R. Schauer (Germany).

Nomenciarllre CommitreeoflUBMB (NC-lUBMB) (those additional tolCBN): A. Bairoch (Switzerland), H. Berman (USA), H. Bielka (Germany), C.R. Cantor (USA), W. Saenger (Germany). N. Sharon (Israel), E. van Lenten (USA). E.C. Webb (Australia).

American Chemical Society Commillee for Carbohydrare Nomenciarure: D. Horton (Chairman), L. Anderson. D.C. Baker, H.H. Baer, J.N. BeMiller, B. Bossenbroek, R. W. Jeanloz, K.L. Loening. W. A. Szarek. R.S. Tipson. W.J. Whelan. R.L. Whistler.

Corresponding Members ofrhe ACS CommillU for Carbohydrare Nomenclature (other than JCBN and the expert panel): R.F. Brady (USA). 1.S. Brimacombe (UK). J.G. Buchanan (UK). B. Coxon (USA). J. Defaye (France). N.K. Kochetkov (Russia), R.U. Lemieux (Canada). R.H. Marchessault (Canada). 1.M. Webber (UK).

Correspondence on these recommendations should be addressed to Dr. Alan D. McNaught at the above address or to any member of the Commission.

Repnxluced from Pure Appl. Chem., 1996.68,1919. Copyright @ 1996 International Union of Pure and A.pplied Chemistry (JUPAC). Published by Elsevier Sci~nce Lid. 2757

NOMENCLATURE OF CARBOHYDRATES (Recommendations 1996)

Contents PrMmble 2-Cmb-O. HistoriCilI deveiopmetll of nomenclature 0.1. Early approaches 0.2. The coatribution of Emil FISCher 03. Cyclic forms 0.4. Nomenclatulecommissions 2-Carb-1. Defmitions and convetllions 1.1. Carbohydrates 1.2. Moaosaccbarides (a1doses and ) 1.3. Dialdoses 1.4. Dikeloses 1.5. Ketoaldoses (aldoketoses) \.6. Deoxy 1.7. Amino sugars 1.8. Alditols 1.9. A1doaic acids 1.1 0_ KetoaIdonic acids 1.11. Uronic acids 1.12. Aldaric acids 1.13. 1.14.0ligosaccharides 1.15. J.16. Conventions for examples 2-Carb-2. Paretll moMsaccharides 2.1. Choice of PaleDt structure 2.2. Numbering and naming of the parent structure 2 ·Carb-3. The Fischer projection of the acyclic form 2-Carb-4. Configurational symbols and prefixes 4_1. UseofDandL 4_2. The configurational atom 4.3. Configurational p!efixes in systematic names 4.4. Racemates and meso forms 4.5. Optical rotation 2-Carb-S. Cyclic fornu and 'heir represemation 5.1. Ring size 5.2. The Fischer projection 5.3. Modified Fischer projection 5.4. The Haworth repre$eIltation 5.5. Unconventional Haworth representations 5.6. The Mills depiction 5.7. Depiction of conformation 5.8. Conformations of acyclic chains 2-Carb-6. AMmeric forms; use of a and 11 6.1. The anomeric centre 6.2_ The anomeric reference atom and the anomeric cOIIfigurationaisymbol 6.3. Mixtures of 6.4_ Use of a and 11 2-Cmb-7. Can/onnalion ofcyclic farms 7.1. The confonnational descriptor 7.2. Notation of ring shape 7.3. Notation of variants 7.4. Enantiomers 2-Carb-8. 8.1. Trivial names 8.2. Systematic names 8.3. Multiple configurational prefixes 2758

8.4. Multiple selS of chira! centres 8.5. Anomeric configuration in cyclic forms of higher aldoscs 2-Carb-9. Dialdoses 2-Carb- 10. KellJses 10.1. Classification 10.2. Trivial names 10.3. Systematic names lOA. Configurational prefixes 2-Carb-J I. Dilatous 11.1. Systematic names 11.2. Multiple sets of chira! centres 2-Carb-J2. Kttloaldoses (aJdoIcetosu. aldosulosu) 12.1. Systematic names 12.2. Dehydro names 2-Carb-J3. lkoxy sugars 13.1. Trivial names 13.2. Names derived from trivial names of sugars 13.3. Systematic names 13.4. Deoxy a1ditols 2-Carb·14. Amino sugars 14.1. Genetal principles 14.2. Trivial names 14.3. SystemaIic names 2-Carb-15. Thio sugars and otMrchakogen aJUZlogues 2·Carb-16. OtMr substituted 16.1. Replacement of at a non-terminal caIbon atom 16.2. Replacement ofOH at a non-terminal atom 16.3. Unequal substitution at a non-tenninal carbon atom 16.4. Tcnninal substitution 16.5. Replacement of cariKmyl by (imines. hydrazones. osazones etc.) 16.6. Isotopic substitution and isotopic labelling 2-Carb-/7. Unsaturated monosaccharides 17.1. General principles 17.2. Double bonds t 7.3. Triple bonds and cunmlative double bonds 2-Carb-18. Branched-chain sugars 18.1. Trivial names 18.2. Systematic names 18.3. Choice of parent 18.4. Naming the branches 18..5. Numbering 18.6. Tcnninal substitution 2-Carb-19. Alditols 19.1. Naming 19.2. muo Forms 2-Carb-20. Aldonic acids 20.1. Naming 20.2. Derivatives 2-Carb-21. Ketoa/Jonic acids 21.1. Naming 21.3. Derivatives 2-Carb-22 Uronic acids 22.1. Naming and numbering 22.2. Derivatives 2-Carb-23. A/dark acids 23.1. Naming 23.2. muo Forms 23.3. Trivial names 23.4. Derivatives 2-Carb-24. O-SubslitutiOIl 24.1. Acyl (alkyl) names 2759

24.2. Phosphorus 24.3. Sulfates 2-Qub-2S. N-Substilution 2-CarlJ-26. Intramolecular anhydrides 2-Carb-27. Intermol«ul.ar anhydrides 2-Carb-28. Cyclic acetals 2-Carb-29. HMliDcetals and hemilhiODCl!tais 2-CarlJ-JO. il.cl!tais. keals and rheir thio analogues 2-Carb-Jl. Names for residues 31.1. Glycosyl residues 31.2. Monosaccharides as substituent groups 31.3. Bivalent and tervalent residues 2-Carb-32. Radicals, cations and anions 2-CarlJ·JJ. Glycosides and glycosyl C()ItI{IOunds 33.1. Definitions 33.2. Glycosides 33.3. Thioglycosides. 33.4. Selenoglyc:osides 335. Glycosyl halides 33.6. N-Glycosyl compounds (gIycosylamines) 33.7. C-GlycosyJ oompounds 2-Carb-J4. Repiac_ of ring oxygen by other ele/fWIIS 34.]. Rep1acement by nitrogen or phosphorus 34.2. Replacemeot by catbon 2-Carb-35. Carbohydrates containing additional rings 35.1. Use of bivalent substituent prefixes 35.2. Ring fusion methods 35.3. Spiro systems 2-CarlJ-36. 36.1. Definition 36.2. Disaccharides without a free hemiacetal 36.3. Disaccharides with a free hemiacetal group 36.4. Trivial names 2·Qub·37. Oligosaccharitks 37.1. Oligosaccllarides without a ftee hemiacetal group 37.2. with a free hemiacetal group 37.3. Branched oligosaccharides 37.4. Cyclic oJigosaccharides 37.5. analogues 2·Carb-J8. Use ofsymbols for defining oligosaccharide Strltcturelf 38.1. General considerations 38.2. Representations of chains 38.3. The extended form 38.4. The condensed foon 385. The short form 2-CarlJ-39. :; 39.1. Names fot homopoJysaccharides 39.2. Designation of configuration of residues 39.3. Designation of linlcage 39.4. Naming of newly discoveml polysaccharides 39.S. Uronic acid derivatives. 39.6. derivatives 39.7. Polysaccharides composed of more than one kind of residue 39.8. Substituted residues 39.9. . proleoglycans and peptidoglyc:ans References A.ppendix Trivial Names (or Caroohydra!es. with their Systematic Equivalents Glossary of Glycose-based Terms 2761

Preamble These Recommendations expand and replace the Tentative Rules for Carbohydrate Nomenclature [1] issued in 1969 jointly by the ruPAC Commission on the Nomenclature of Organic Chemistry and the IUB-ruPAC Commission on Biochemical Nomenclature (CBN) and reprinted in [2]. They also replace other published JCBN Recommendations [3-7] that deal with special~ areas of carbohydrate lenninology; however, these documents can be consulted for further examples. Of relevance to the field, though not incOlporated into the present document, are the following recommendations: Nomenclature of cyclitols, 1973 [8] Numbering of atoms in myo-inositol, 1988 [9] Symbols for specifying the conformation of polysaccharide chains, 1981 nO] Nomenclature of gIycoproteins, glycopeptidcs and peptidoglycans, 1985 [II] Nomenclature of , in preparation [12J The present Recommendations deal with the acyclic and cyclic forms of monosaccharides and their simple derivatives, as well as with the nomenclature of oligosaccharidcs and polysaccharides. They are additional to the Definitive Rules for the Nomenclature of Organic Chemistry [13,14] and are intended to govern those aspects of the nomenclature of carbohydrates not covered by those rules.

2~Carb-O. Historical developlMnt ofcarbohydrate nomenclature [15] 2-Carb-O.l. Early approaches In the early nineteenth century, individual sugars were often named after their source. e.g. grape sugar (fraubenzuclc:er) for , cane sugar (RoIuzucker) for saccharose (the name was coined much later). The name glucose was coined in 1838; KekulC in 1866 proposed the name 'dextrose' because glucose is dextrorotatory, and the laevorotatory 'fruit sugar' (Fruchtzuck:er, ) was for some time named 'Iaevulose' (American spelling 'levulose'). Very early, consensus was reached that sugars should be named with the ending '~', and by combination with the French word 'cellule' fl:?r cell the term was coined, long before the structure was known. The term 'carbohydrate' (French 'hydrate de carbone') was applied originally to monosaccharides, in recognition of the fact that their empirical composition can be expressed as C,.{H20)n. However the term is now used generically in a wider sense (see 2-Carb-I.l). 2-Carb-O.2. The contribution of Emil FIscher Emil Fischer [16} began his fundamental studies on carbohydrates in 1880. Within ten years, he could assign the relative configurations of most known sugars and had also synthesized many sugars. This led to the necessity to name the various compounds. Fischer and others laid the foundations of a terminology still in use, based on the terms , , , and . He endorsed Armstrong's proposal 10 classify sugars into aldoses and ketoses, and proposed the name fructose for laevulose, because he found that the sign of optical rotation was not a suitable criterion for grouping sugars into families. The concept of stereochemistry, developed since 1874 by van't Hoff and i.e Bel, had a great impact on carbohydrate chemistry because it could easily explain isomerism. Emil Fischer introduced the classical projection formulae for sugars, with a standard orientation (carbon chain vertical, carbonyl group at the top); since he used models with flexible bonds between the atoms, he could easily 'stretch' his sugar models into a position suitable for projection. He assigned to the dextrorotatory glucose (via the derived glucaric acid) the projection with the OH group at C-5 pointing to the right, well knowing that there was a 50% chance that this was wrong. Much later (Bijvoet, 1951), it was proved correct in the absolute sense. Rosanoff in 1906 selected the enantiomeric glyceraIdehydes as the point of reference; any sugar derivable by chain lengthening from what is now known as n-glyceraJdehyde belongs to the 0 series, a convention still in use. 2-Carb-O.3. Cyclic forms Towards the end of the nineteenth century it was realized that the free sugars (not only the glycosides) existed as cyclichemiacetals or hemiketals. , discovered in 1846 by Dubrunfaut, was now interpreted as being due to a change in the configuration oCthe glycosidic (anomeric) carbon atom. Emil Fischer assumed 2762

the cyclic form to be a five-membered ring. which Tollens designated by the symbol < I ,4>, while the six-membered ring received the symbol <1,5>. In the 19205, Haworth and his school proposed the terms '' and '' for the two forms. Haworth also introduced the 'Haworth depiction' for writing structural formulae, a convention that was soon widely followed. 2·Carb·0.4. Nomenclature commissions Up to the 1940s, nomenclature proposals were made by individuals; in some cases they were followed by the scientific conununity and in some cases not. Official bodies like the International Union of Chemistry, though developing and expanding the Geneva nomenclature for organic compounds, made little progress with carbohydrate nomenclature. 1be lUI'AC Commission on Nomenclature of Biological OIemistry put forward a classification scheme for carbohydrates, but the new terms proposed have not survived. However in 1939 the American OIemicaJ Society {ACS} formed a committee to look into this matter, since rapid progress in the field had led to various misnomers arising from the lack of guidelines. Within this commit,tee, the foundations of modem systematic nomenclature for carbohydrates and derivatives were laid: numbering of the sugar chain. the use of D and L and ex and 13, and the designation of stereochemistry by italicized prefixes (multiple prefixes for longer chains). Some preliminary conununications appeared, and the final report, prepared by M.L. Wolfrom, was approved by the ACS Council and published in 1948 [11]. Not all problems were solved, however, and different usages were encountered on the two sides of the Atlantic. Ajoint British·American committee was therefore set up, and in 1952 it published 'Rules for Carbohydrate Nomenclature' [18J. This work was continued, and a revised version was endorsed in 1963 by the American Chemical Society and by the Chemical Society in Britain and published [19J. The publication of this report led the lUI'AC Commission on Nomenclature of Organic Chemistry to consider the preparation of a set of IUl'AC Rules for Carbohydrate Nomenclature. This was done jointly with the IUPAC·IUB Commission on Biochemical Nomenclature, and resulted in the 'Tentative Rules for Carbohydrate Nomenclature, Part I, 1969', published in 1971n2 in several journals [1]. It is a revision of this 1971 document that is presented here. In the present document, recommendations are designated 2-Carb-n, to distinguish them from the Carbon recommendations in the previous publication. 2-Carb-l. Definitions and conventions 2·Carb·l.l. Caroohydrates 1be generic term 'carbohydrate' includes monosaccharides, oligosaccharides and polysaccharides as well as substances derived from monosaccharides by reduction oftbe carbonyl group (a1ditols), by oxidation of one or more tenninal groups to carboxylic acids, orby replacement of one or more hydroxy group(s) by a hydrogen atom, an amino group, a !hiol group or similar heteroatomic groups. It also includes derivatives of these compounds. The term 'sugar' is frequently applied to monosaccharides and lower oJigosaccharides. It is noteworthy that about 3% of the compounds listed by Chemical Abstracts Service (i.e. more than 360 (00) are named by the methods of carbohydrate nomenclature. Note. Cyclitols are generally not regarded as carbohydrates. Their nomenc1ature is dealt with in odaer recommendations [8,9]. 2-Carb·l.2. Monosaccharides Parent monosaccharides are polyhydroxy aldehydes H·[CHOH)....cHO or polyhydroxy H·[CHOH],,· CO·[CHOH]m·H with three or more carbon atoms. The generic term 'monosaccharide' (as opposed to oligosaccharide or polysaccharide) denotes a single unit, without glycosidic connection to other such units. It includes a1doses, dialdoses, a1dolcetoses, ketoses and diketoses, as well as deoxy sugars and amino sugars, and their derivatives, provided that !he parent compound has a (potential) carbonyl group. 1.2.1. Aidoses and ketoses Monosaccharides with an aldehydic carbonyl or potential aldehydic carbonyl group are called a1doses; those with a ketonic carbonyl or potential ketonic carbonyl group, ketoses.

Note. The term 'potential aldehydic carbonyl group' refea 10 the hemiacetal group arising from ring closure. Likewise, the term 'potentiallo:elonic carbonyl group' refers 10 the hemilcetal structure (see 2-Carb-5). 2763

1.2.2. Cyclicfomrs Cyclic hemiacetals or hemiketals of sugars with a five-membered (tetrahydrofuran) ring are called , those with a six-membered (tetrahydropyran) ring . For sugars with other ring sizes see 2-Carb-5. 2-Carb·l.3. Dlaldoses Monosaccharides containing two (potential) aldehydic carbonyl groups are called dialdoses (see 2-Carb-9). 2-Carb-l.4. Diketoses Monosaccharides containing two (potential) Icetonic carbonyl groups are termed diketoses (see 2-Carb-11). 2-Carb-l.5. Ketoaldoses (aldoketoses, aldosuloses) Monosaccharides containing a (potential) aldehydic group and a (potential) Icetonic group are called ketoaJd­ oses (see 2-CaIb-12); this term is preferred to the alternatives on the basis of 2-Carb-2.1.1 ( preferred to ). 2-Carb·I.6. Deoxy sugars Monosaccharides in which an alcoholic hydroxy group has been replaced by a hydrogen atom are called deoxy sugars (see 2-Carb-I3). 2-Carb-l.7 Amino sugars Monosaccharides in which an alcoholic hydroxy group has been replaced by an amino group are called amino sugars (see 2-Carb-14). When the hemiacetal hydroxy group is replaced. the compounds are called glycosyl­ amines. 2-Carb-l.8. Alditols The polybydric alcohols arising formally from the replacement of a carbonyl group in a monosaccharide with a CHOH group are termed alditols (see 2-Carb-19). 2-Carb-I.9. Aldonic acids Monocarboxylic acids formally derived from aldoses by replacement of the aldehydic group by a carboxy group are termed aldonic acids (see 2-Carb-20). 2-Carb-l.lO. Ketoaldonic acids Oxo carboxylic acids formally derived from aldonic acids by replacement of a secondary CHOH group by a carbonyl group are called ketoaldonic acids (see 2-Carb-21). 2-Carb-l.lI. Uronic acids Monocarboxylic acids formally derived from aldoses by replacement of the Cll20H group with a carboxy group are termed uronic acids (see 2-Carb-22). 2-Carb·l.l2. Aldaric acids The dicarboxylic acids formed from aldoses by replacement of both terminal groups (CHO and CHlOH) by carboxy groups are called aldaric acids (see 2-Carb-23). 2-Carb·1.l3. Glycosides Glycosides are mixed acetals formally arising by elimination of between the hemiacetal or hemiketal hydroxy group of a sugar and a hydroxy group ofa second compound. The bond between the two components is called a .. For an extension of this definition, see 2-Carb-33. 2-Carb-I.14.0Iigosaccharides Oligosaccharides are compounds in which monosaccharide units are joined by glycosidic linkages. According to the number of units, they are called disaccharides. , , pentasaccbarides etc. The borderline with polysaccharides cannot be drawn strictly; however the term 'oligosaccharide' is commonly used to refer to a defined structure as opposed to a polymer of unspecified length or a homologous mixture. When the linkages are of other types, the compounds are regarded as oligosaccharide analogues. (See 2-Carb-37.) 2764

Note. This definition is broader than that given in [6), to rcfIect cunent usage. 2-Cam-US. Polysaccharides 'Polysaccharide' () is Ihe name given to a macromolecule consisting of a large number of monosac­ charide (glycosc) residues joined to each other by glycosidic linkages. The term poly(glycose) is not a full synonym for polysaccharide (glycan) (cf. [20)). because it includes macromolecules composed of g1ycose residues joined to each other by non-glycosidic linkages. For polysaccharides containing a substantial proportion of amino sugar residues, !he term polysaccharide is adequate. aIlhough Ihe term g1ycosaminoglycan may be used where particular emphasis is desired. Polysaccharides composed of only one kind of monosaccharide are-described as homopolysaccharides (homoglycans). Similarly. if two or more different kinds of monomeric unit are present. !he class name heteropolysaccharide (heteroglycan) may be used. (See 2-Carb-39.) The term 'glycan' has also been used for !he saccharide component of a , even Ihough Ihe chain length may not be large. TIle term polysaccharide has also been widely used for macromolecules containing glycose or a1ditol residues in which both glycosidic and phosphate diester linkages are present. 2-Carb-l.l6. Conventions for examples 1.16.1. Names of examples are given wilh an initial capital letter (e.g. 'L-glycero-p-D-gluco-Heptopyranosc') to clarify !he usage in headings and to show which letter controls die ordering in an alphabetical index. 1.16.2. The following abbreviations are commonly used for substituent groups in structural formulae: Ac (acetyl), Bn or PhCH2 (benzyl). Bz or PhCO (benzoyl). Et (ethyl). Me (methyl). Me3Si (not TMS) (trlmethylsilyl). ButMClSi (notTBDMS) (teN-butyldimethylsilyl), Ph (phenyl). Tf(triflyl = trifluorornetbane­ sulfonyl), Ts (tosyl = toluene-p-sulfonyl), Tr (trityl). 2-Carb-2. Parent monosaccharides 2-Carb·2.1. Cboice of parent structure In cases where more Ihan one monosaccharide structure is embedded in a larger molecule, a parent structure is chosen on die basis of !he following criteria. applied in the order given until a decision is reached: 2.1.1. The parent Ihat includes die functional group most preferred by general principles of organic nomenclature [13.14]. If!here is a choice. it is made on the basis of the greatest number of occurrences of !he most preferred functional group. Thus a1daric acid > uronic acidlketoaldonic acid/aldonic acid> dialdose > ketoaldosclaldose > diketose > ketose. 2.1.2. The parent with die greatest number of carbon atoms in thc chain. e.g. a rather !han a hexose. 2.1.3. The parent with !he name that comes fIrSt in an alphabetical listing based on: 2.1.3.1. the trivial name or die configurational prefix(es) of !he , c.g. rather Ihan glucose. a gluco rather !han a gulo derivative; 2.1.3.2. the configurational symbol 0 rather !han L ; 2.1.3.3. the anomeric symbol a rather than p. 2.1.4. The parent with the most substituents cited as prefixes (bridging substitution, c.g. 2.3-0-. is regarded as multiple substitution for this purpose). 2.1.5. TIle parent with the lowest locants (see (14], p. 17) for substituent prefIXes. 2.1.6. The parent with die lowest locant for the first-cited substituent. Thc implications of these reconunendations for branched-cllain structures are exemplified in 2-Carb-18. Note 1. To mainrain homomorphic relationships between classes of sugars. the (potential) aldehydc group of a uronic acid is regarded as the principal function foe numbering and naming (see 2-CaJb..2.2.1 and 2-Catb-22). Note 2. To maintain integrity of carbohydrate names. it is sometimes helpful to overstep the strict order of principal group JlIdemK:e lpCCiflCd in general organic: nornencIatum [13.14]. For example, a carboxymethyl-substituted sugar can be named as such, rather than as an derivative (see 2-Carb-31.2). 2765

2-Carb-2.2. Numbering and naming the parent structure The basis for the name is the structure of the parent monosaccharide in the acyclic form. Charts ( and IV (2-Carb-lO) give trivial names for parent aldoses and ketoses with up to six carbon atoms. 2-Carb-S.2 and 2-Carb-l0.3 describe systematic naming procedures.

CHO CHO H-C-OH HO-C-H H-C-OH H-C-OH C~OH CHzOH o-ErythroSG o-ThreOSB D-6/)'U>IO D·lhroo

CHO plO CHO CHO H-C-OH Ho-C-H H-C-OH Ho-C-H H-C-OH H-C-OH HO-C-H HD-C-H H-C-OH H-C-OH H-C-OH H-C-OH CH,OH CH,OH ~ CH,OH D· D- o-Xy1oSG D- D·tIbo o-ataIIOto (D·Rib) (o-Ara) (~~ (~~

CHO CHO CHO CHO CHO CHO CHO '(HO H-C-OH Ho-C-H H-C-OH Ho-C-H H-C-OH HO-C-H H-C-OH HO-C-H H-C-OH H-C-OH HO-C-H HO-C-H H-C-oH H-C-OH HO-C-H HO-C-H H-C-OH H-C-OH H-C-OH H-C-OH HO-C-H HO-C-H HO-C-H HO-C-H H-C-OH H-C-OH H-C-OH H-C-OH H-C-OH H-C-OH H-C-OH H-C-oH bi.oH C~H CH.OH CH,OH 6HzOH CH,oH CH.OH CH.oH D·Allose o-Allrose o-Gfucose O- o-Gufose D~dose O-GaIacIOSG o- o·aUo o-a/lro o·(}Iuco D-manno o·gu/o D-ido r>-gaJacto O·lalo (o.All) (o-AlI) (o-Glc) (D-Man) (o-Gul) (D-Ido) (o-Gal) (D·Tal)

, Chart I. Trivial names (with recommended three-letter abbreviations in parentheses) and structures (in the aldehydic. acyclic fonn) of the aldoses with three to six carbon atoms. Only the D-forms are shown; the L-fonns are the minor images. The chains of chiral atoms delineated in bold face correspond to the configurational prefixes given in italics below the names

2.2.1. Numbering The carbon atoms of a monosaccharide are numbered consecutively in such a way that: 2.2.1.1. A (potential) aldehyde group receives the locant 1 (even if a senior function is present, as in uronic acids; see 2-Carb-2.1. note I); 2.2.1.2. The most senior of other functional groups expressed in the suffix receives the lowest possible locant. i.e. (derivatives) > (potential) ketonic carbonyl groups. 2.2.2. Clwice ofparenl1llJl1fe The name selected is that which comes first in the alphabet (configurational prefixes included). Trivial names are preferred for parent monosaccharides and for those derivatives where all stereocentres are stereochemically unmodified. 2766

Examples: yHzOH

I HOCHHCOH } yttzoH H1:o l-g1uco- HOCH I HCOH HOCH I I HOfH HcxrH } L-erythro _ HOCH HOCH I I CH,oH CH,OH l-Glucilol L-erythfD-{.-gluco-Non-5-u1ose not o-guJitol not o-throo-o-afb.non-S-ulose 2.2.3. Choice between altenwtive nomes for substituUd derivatives When the parent structure is symmetrical, preference between alternative names for derivatives should be given aceording to the following criteria, taken in order: 2.2_3_1. 111e name including the configurational symbol D rather than L. Example: y~H HCOH I HOCH I HCOMe I CH"OH 4-O-Methyt-o-xytitol not 2-O-fnethyt-l-xytitol 2.2.3.2. The name that gives the lowest set of locants (see {I41, p. 17) to the substituents present. Example: ?HzOH MeOCH I MeOCH I HCOH I HCOMe I CH,OH

2,3,5-Tri-O-methyt-o-mannltol not 2,4,5-lri-O-melhyl-o-mannitol 2.2.3.3. The name that, when the substituents have been placed in alphabetical order, possesses the lowest locant for the first-cited substituent. Example: yHzOH AcO«H HOCH I HYDH HCOMe I C~H 2-O-AceIy\-5-O-me-o-mannitol not S-o-acetyt-2-O-melhy\-o-mannltol 2-Carb-3. The Fischer projection ofthe acyclic form In this representation of a monosaccharide, the carbon chain is written vertically, with the lowest numbered carbon atom at the top. To define the stereochemistry, each carbon atom is considered in tum and placed in the plane of the paper_ Neighbouring carbon atoms are below, and the H and OH groups above the plane of the paper (see below). 2767

~ ,. I I I H$OH . H-C-OH H-C-OH . H-C-OH HCOH ! I I I ~OH

(a) (b) (e) (d) (e) (I) (9)

Convenlional representation of a carbon atom (e.g. C-2 of o-glucose) in the FISCher projection. Representation (e) wil be used in general in the present document. The fonnula below is the Fischer projection for the acyclic fonn orD-glucose. The Fischer projections of the other a1doses (in the acyclic fonn) are given in Chart I (2-Carb-2.2).

'cHO 21 HCOH 31 HOCH .1 HCOH 51 HCOH ~ o-Glucose Note. The Fischer projection is not intended to be a true representation of conformation. 2-Carb-4. Configuratiotud symbols and prefixes 2-Carb-4.1. Use of D and L The simplest aldose is (occasionally called gJyceral (21)). It contains one centre of chirality (asynunetric carbon atom) and occurs therefore in two enantiomeric forms. called D-glyceraldehyde and L-glyceraldehyde; these are represented by the projection Connulae given below. It is known that these projections correspond to the absolute configurations. The configurational symbols D and L should appear in print in small-capital roman letters (indicated in typescript by double underlining) and are linked by a hyphen to the name of the sugar.

?HO roo H-

, o-Glyceraldehyde L-Glyceraldehyde 2-Carb-4.2. The configurational atom

A monosaccharide is assigned to the D or the L series according to the configuration at the highest-numbered centre of chirality. This asymmetrically substituted carbon atom is called the 'configurational atom'. Thus if the hydroxy group (or the oxygen bridge of the ring fonn; see 2-Carb-6) projects to the right in the Fischer projection, the sugar belongs to the D series and receives the prefix D-. Examples:

CliO 1 CHO HOCH I 1 HCOH CHO HOCH I 1 I HOCH HCOH HCOH I 1 1 HCOH HOCH HOCH 1 1 1 HCOH HCOH HCOH I 1 1 CH.oH CH,OH CHoOH o-Glucose o-Xyfose o-ambino-Hex-2-ulose o-glycel"lH-gulo-Heptose (D-Fructose) o Monosaccharides 2768

CHO I COO yHoOH HOCH I I HOCH CHO C=O I I I HOCfH HCOH HCOH HOCH HCOH I I I HOCH HCOH H60H HO

L-Glucose l-Arabinose L-xy/o-Hex-2-uIose L-gl]lcelt>O-manno+teptose (L -SoIbose) l Monosaccharides 2-Carb-4.3. Configurational pref'lXes in systematic names In the systematic names of sugars or their derivatives, it is necessary to specify not only the configuration of the configurational atom but also the configurations of all CHOH groups. This is done by the appropriate configurational prefIX. These prefixes are derived from the trivial names of the a1doses in Chart I (relevant portions of the struClW'es are delineated in bold face). In monosaccharides with more than four asymmetrically substituted carbon atoms, where more Ihan one confagurational prefix is employed (see 2-Carb-B.3), each group of asymmetrically substituted atoms represented by a particular prefix has its own configurational symbol, specifying the configuration (0 or L) of the highest numbered atom of the group. The configuratiOllai prefixes are printed in lower-case italic (indicated in typescript by underlining), and are preceded by either J)- or L-, as appropriate. For examples see 2-Carb-4.2 and 2-Carb-6.2 Note. In cyclic forms of sugars, the configuration at !he anomcric cbiral centre is defmed in relation to the 'anomeric reference atom' (see 2-Ca!b-6.2).

2-Carb-4.4. Racemates and m~so forms Racemates may be indicated by the prefix DL-. Structures that have a plane of symmetry and are therefore optically inactive (e.g. erythritol, galactitol) are called muD forms and may be given the prefix 'meso-'. 2-Carb-4.S. Optical rotation If the sign of the optical rotation under specified conditions is to be indicated, this is done by adding (+)- or (-)- before the configurational prefix. Racemic forms are indicated by (±)-. Examples: o-GIucose or (+).o-glucose o-Fructose or (-)-D-fructose DL-Glucose or (±)-glucose

Z-Corb-S. Cyclic forms tmd their rep,u~ntatio" 2-Carb-S.l. Ring size Most monosaccharides exist as cyclic hemiacetals or hemiketals. Cyclic forms with a three-membered ring are called oxiroses, those with a four-membered ring oxetoses, those with a five-membered ring furanoses, with a six-membered ring pyranoses, with a seven-membered ring septanoses, with an eight-membered ring octanoses, and so on. To avoid ambiguities, the locants of the positions of ring closure may be given; the locant of the carbonyl group is always cited first, that of the hydroxy group second (for relevant examples of this see 2-carb-6.4). Lack of ring size specification has no particular implication. Note. The '0' of oxirose, oxetose. and oclanose is not elided after a prefIX ending in '0'. Exafl1Jle: Nonooctanose, not nonodanose. If it is to be stressed that an open-chain fonn of an aldose is under consideration, the prefix 'aIdelrydo-' may be used. For ketoses, the prefix is 'uro-' 2769

2-Carb-S.2. The Fischer projection If a cyclic fonn of a sugar is to be represented in the Fischer projection. a long bond can be drawn between the oxygen involved in ring formation and the (anomeric) carbon atom to which it is linked, as shown in the following fonnulae for cyclic forms of (l-D-glucose {see 2-Carb-6 for the meaning of (l and ~):

Hfo~ []OH I HCO HCOH HCOH HCOH I I I I HOCH OCH HOCH HOCH HOCH I I I HCOH HCoH HCO HCOH H?OH I I I "~ I tJ HCOH HCOH HCOH HCO HCOH I , I I I ~ CHtOH cHtQH CH,OH CH,OH CH20 a-D-Glucooxirose a-o-Glucooxetose a-D-Glucofuranose a-D-Glucopyranose a-o-Glucoseptanose 2-Carb-S.3. Modified Fischer projection To clarify steric relationships in cyclic forms. a modified Fischer projection may be used. The carbon atom bearing the ring-fonning hydroxy group, Con (C-S for glucopyranose) is rotated about its bond to C-{n - I) (C-4 for glucopyranose) in order to bring all ring atoms (including the oxygen) into the same vertical line. The oxygen bridge is then represented by a long bond; it is imagined as being behind the plane of the paper. Examples are given below.

HCOH HCOH I I HOCH HOY-CHtOH HCOH HCOH I I I HCOH HOCH HOCH HCOAe I I I I HCOH HCOH HCOH AcOCH OAe I I I I I HOCH2- H HOC~-?H HC-C-H Hy-C~ y I 'cHtOAc o

a·D-Glucopyranose 2,3,5,6-Tetra-O-acetyl­ jJ-L -Fucopyranose jJ-o-Fructoluranose a-D-galaclofuranose Thus the trans relationship between the hydroxymethyl group and the C-I hydroxy group in (l-D-glucopyran­ ose, and the cis relationship between the methyl group and the Col hydroxy group in ~-L-fucopyranose, are clearly shown. Note that representation of ketoses may require a different modification of the Fischer projection, as shown in the fructofuranose example above. Here C-2 is rotated about the bond with C-3 to accommodate the long bond to C-2 from the oxygen at CoS. 2-Carb-S.4 The Hawortb representation This is a perspective drawing of a simplified model. The ring is orientated almost perpendicular to the plane of the paper, but viewed from slightly above so that the edge closer to the viewer is drawn below the more distant edge, with the oxygen behind and C-I at the right-hand end. To derme the perspective, the ring bonds closer to the viewer are often thickened. The following schematic representation of pyranose ring closure in D-glucose shows the reorientation at C-5 necessary to allow ring formation; this process corresponds to the change from Fischer to modified Fischer projection.

'CHO I HCOH I HOCH I H.OH HCOH I HCOH r 6CHzOH Haworth representation of o-glucopyranose The orientation oflhe model described above results in a clockwise numbering of the ring atoms. Groups that appear to the right of the modified Fischer projection appear below the plane of the ring; those on the left 2770

appear above. In the common Haworth representation of the pyranose fonn of D-a1dohexoses, C-6 is above the plane. Generally, the configuration at the centre that yields the ring oxygen detennines whether the rest of the carbon chain is below or above the plane of the ring.

ElCampJes (tor the use of a and p see 2.carb~:

HCOH HCOH I H{:oH HCOH I =' OHH, HOCH - HOCH I [A'I ~Hz. ~OH HCOH OCH Ht-CHzOH I , 5 ~H OH CH.oH 5 G' ;: FISCher mod"lfied Haworth 1JCHzO Fischer !k-Arabinofuranose representations P-O-Ribopyranose 0P0 2- b0~H ~~ HO OH p-o-Riboluranose 5-phosphale

QPO,Z­ I H CH.oH o CHz-0P032- HOC~~~ H HO HCOH H HO ~ I HO~ OH OH H HfOH HO H CHzO OH H a-o-Fructopyrenose cx-o-Fructofuranose 1.6-bisphosphate

OH

H H ~ItO ItO OH H

Methyl a-o-glucoseptanoside If'ioOH HOCH I HOCH, HOCH

H~l'r H Methyl m-L-aIIrooxetoslde MeIhyI IH>-a11ooxJroslde Note. In writing Haworth fonmlae, the H atoms bound to the carbon atoms of the rinB are often omitted 10 avoid crowding oCtile lettering in the ring. For the sake ofcluily, the fonn with H atoms included is prefemd in this document. 2-Carb-S.5. Unconventional Haworth representations It is sometimes desirable to draw Haworth Connulae with the ring in other orientations (sec Chart ll), when there are bulky substituents to be represented, or when linkages in oligo- or poly-saccharides are to be shown. If the ring is inverted [as in (g)-(I)), the numbering runs countercloclcwisc. 2771

OH H

H~OHH~H HO CI¥>H . 0 OH H H H HO OH • HO~~>~ H . HO~ 0 H H OH OH H H (a) (h) (e) OH H HOC4}0~H ~H HO OH H H o ~HH H H H HO OH

H OH OH H lei) (e) (I) ~: f~~~ t, :~ ~~ OH H H ~H CH,OH (g) (II) (i)

O~H:HH H HO OH ~"~~ 1 OH H H OH (j) (1<) (I) Chart U. Il-o-Glucopyranose in the twelve possible Haworth representations (the hydrogen atoms are frequently omitted) 2-Carb-5.6. The Mills depiction In some cases, particularly where additional rings are present, structural fonnulae can be clarified by use of the Mills depiction. Here the main hemiacetal ring is drawn in the plane of the paper; dashed bonds denote substituents below this plane, and thickened bonds those above. Examples: C~ o -0 I ~_ \ Me.c-..o 'b"-CMe,z ~HO 0 l,2:3,4-Di-O-lsopropylldene-«-o-galadopyranose o-Glucaro-l,4:6,3-dlactone 2-Carb-5.7. Depiction of conformation The Haworth representation implies a planar ring. However, monosaccharides assume conformations that are not planar: these may be represented by Haworth conformational fonnulae. The nomenclature of confonna­ tions is described in 2-Carb-1. For example, ll-o-g1ucopyranose assumes a chair confonnation:

H HO~O\ OH HO~OH OH H H

p-D-Glucopyranose in a chair conformation 2772

Note. The hydrogen atoms bonded to carl>on are frequently omitted. but their inclusion may be necessary to make a stereochemical point. 2-Carb-5.8_ Conformations of acyclic chains Conformational depictions of acyclic sugar chains are conveniently expressed by locating certain atoms in the plane of the paper and orientating the remaining atoms or groups appropriately above and below that plane. as shown for D-arabinitol and xylitol (it should be recognized that the favoured conformation does not necessarily have all the carbon atoms in the same plane):

HO H \1 HOCH2 .... c, /OH ..... c.... C /\ /\ H6 H H CH,OH

o-Arabinitol Xytilol

2-Carb-6_ Anomeric forms; use of IX and ~ 2-Caro-6.1. The anomeric centre The new centre of chirality generated by hemiacetal ring closure is called the anomeric centre. The two stereoisomers are referred to as anomers, designated IX or ~ according to the configurational relationship between the anomeric centre and a specified anomeric reference atom.

2-Carb-6.2. The anomeric reference atom and the anomeric configurational symbol (IX or ~) The anomeric reference atom is theconfigurational atom (see 2-Carb-4.2and 4.3) oCthe parent. unless multiple configurational prefixes (see 2-Carb-8.3) are used. If multiple configurational prefixes are used, the anomeric reference atom is the highest-numbered atom of the group of chiral centres next to the anomeric centre that is involved in the heterocyclic ring and specified by a single configurational prefix. In the IX , the exocyclic oxygen atom at the anomeric centre is formally cis, in the Fischer projection, to the oxygen attached to the anomeric reference atom; in the ~ anomer these oxygen atoms are fonnally trans.

The anomeric symbol IX or P. followed by a hyphen, is placed immediately before the configurational symbol D or L of the trivial name or of the configurational prefix denoting the group of chiral carbon atoms tl!at includes the anomeric reference atom. Examples:

I I HCOH HCOH H H I HOfH HOCH ~~I OH H HCOH HO~H HOH HCOH HO H I =~HCO ==>~H60 I H OH I H OH tlCH;!DH © ~OH '0 a-o-gluco Il-rrgluco a-D-Glucopyranose p-D-Glucopyranose

H MeOCH I HCOH HO 0Me HCOMe I H· I HOCH - HCOH I H oli H H OH H =~HOCH I ~-~H H OMe r ~H OH ~ ~H OH 0 0~ a-t.-BlBbino Il-t.-threo Methyl a-t.-arabinopyranoside Methyl jl-t.-threoluranoside 2773

CHzOH I

tH H:OH 0 H HCOH t Q ONe OH HOCH H~O {f, OH H I HO 0Me oyti HCOH H ~ -HCOH H H I I H OH CH,OH cHzOH

Maocr~CH,OHHOCH HOCIiz 0 OMe HfoH = ~-~ ~ -lHfo H"i----Y" bH,OH CHzOH' OH H

jl-D-SIlIbino Methyljl-D-fructofuranoside ~~COOM8 HCOH OH OH ~I AcNHCH I - HOCHz\-r--O---JCOOMe OCH I -HCOH AcNH~ ~HtOH OH I ClizOH

D-~ Methyl 5-acetamido-3.5-dideoXY-D-g~D-gaJacto-non-2-u1opyranosonate (see 2-CaIb-14.2)

-+ denotes the anomcric reference atom; ~ denotes the configurational atom. Note. For simple aldoses up to aldobexoses. and ketoSeS up to hept-2-uloses, the aoomeric reference alom and the configuralional atom IUe the same. 2-Carb-6.3. Mixtures of Boomers In solution. most simple sugars and many of their derivatives occur as equilibrium mixtures of tautomers. 1be presence of a mixture of two anomers of the same ring size may be indicarcd in the name by the notation a.jl-. c.g. a.jl-D-glucosc. In formulae. the same situation can be expressed by separating the representation of the ligands at the anomeric centre from thc a. and ~ bonds [see examples (a) and (c». or by use of a wavy line [(b) and (d)] (particularly if hydrogen atoms IUe omitted).

~:

9P032- QPO:st,. I c~IHz0 CHzOH ~O~ H HO ~~~>K~ H ICHzQHoOH or . W H OH H OH HO H HO H (a) (b) (el (d)

a.P-D-Fructofuranose 6-phosphate 2774

2-Carb-6.4. Use of a and P The Greek letters a: and P are applicable only when the anomeric cari>on atom has a lower loeant than the anomeric reference atom. In the case of dialdoses (cf. 2-Carb-9). some diketoses (cr. 2-Carb-ll) and aldoketoses (cr. 2-Carb-12), ring closure is also possible in the other direction, i.e. of a cari>onyl group with a higher Joean! than the reference carbon atom with a hydroxy group having a lower locani. In this case, the configuration of the anomeric carbon atom is indicated by the appropriate symbol R or S according to the sequence rule (cc. Section E in [13). Examples:

1 CHO HOho--} 2 sf1::"-+OH OHOH 3

(SR)-o-gluco-Hexodiald0-6,2-pyranose (S5)-1,2-Q-lsopropyfidene-ex-D·gfuco-hexodialdo- 1,4:S,3-difuranose Note that locant numerals (potential carbonyl first) may be needed before the ring-size suffix in such cases. 2-Carb-7. Confomuzlion ofcyclic forms* 2-Carb·7 .1. The conformational descriptor The conformation, i.e. the (approximate) spatial arrangement of the ring atoms of a monosaccharide in the cyclic form, may be indicated by an italic capital letter designating the type of ring shape, and numerals, distinguishing the variants. The conformational descriptor is joined to the end of the name of the monosac· charide by a hyphen. Example:

Table 1. Conformations and their notations; some examples are shown in Chart ill

Type of sugar Conformation Atoms of refeRllcc plane AbovepJanc Belowplanc Noration Example

A1dotUranosc envelope 0-4.C-I.C-3,C-4 C-2 1>2 AldotUranosc envelope C-I,C-2.C-4,O-4 C-3 3£ 2 Aklofunonose twist C-I,0-4,C-4 C-3 C·2 372 3 A1dofuraoose twist C-3,C-4,O-4 C-2 C-l 71 4 Aldopyranose chair C-2,C.3.C·S,Q-S C-4 C-l ·CI 5 Pynmoid lactone chair C-2,C-3.C-S,O-S Col C-4 1(4 6 A1dopyranose boat Q-S,C-l.C-3,C-4 C-2,C-S "UB 7 Aldopyranose boat C.2,C-3,C-S,Q-S C-I,C-4 BI,4 8 Alclopyranosc skew C-Z,C-4.C-S,O-S C-l C·) IS) \I AldopynllOSO skew C-l,C-3,C-4.C-5 C-2 O-S 2S0 10 Aidopyrlllosc haIf-dlair C-l,C-2,C-3,C-4 C-S S--S 'Hs 11 Pyranoid IlICtone envelope C-l,C-2.C-3.C-4,Q-S C-S 'E 12

This is an abridged version of the document 'Coofunnational Nomenclalure for Five- and Six-membered Ring Forms ofMoaosaccharides and their Derivatives. Recommendations 1980 (3}. 2775

2 3

H ,0

HelCH:! "~\\IQ ¥ ";" OH '00 H H

4 5 6

H ,. .. H

HO OH "w7 8 9

10 11 12

1 Methyl p·f}-mbinofuranoside·El 2 a-[).Anbinofunmose-3E 3 1,2-0-Isopropylidcne-/l-t.-idofuranosc-3Tz 4 2,3-0·lsopropylidene--aUopyranose-B, •• 9 l.;l-O-Ethylidene-a-l>-glucopyranose-' S3 10 /l-L-All!'oPyranosc-250 11 Methyl 2.3-lIIIhydro-.5.lhio-/l-t.-lyxopynmoside-'Hs 12 2,3-Dideoxy-lH:rylhro-hex-2...... ono-l,5-1actonc-'E Chart m. Drawings of the conformations listed in Table 1. The reference plane is stippled.

2-Carb-7.2.. Notation of ring shape The appropriate letters are as follows. Five-membered rings: E for envelope and T for twist; six-membered rings: C for chair, B for boat, S for skew, H for half-chair, and E for envelope. Examples are given in Oiart m. 2-Carb-7..3. Notation ofvariants The variants are distinguished by the locants of those ring atoms that lie outside a reference plane (defined below) and are listed for some examples in Table 1. The locants of ring atoms ttiat lie on the side of the reference plane from which numbering appears clockwise (i.e. the upper side in the normal Haworth representation of furanoses and pyranoses) are written as superscripts and precede the letter; those that lie on the other side are written as subscripts and follow the letter. Heteroatoms (e.g. 0, 'S) are indicated by their subscript or superscript atomic symbols. Table 1 gives the notations and ClJart ill some examples. 2776

Six-membered rings Chnirs. The reference plane is defined by two panlilel ring sides. so chosen that the lowest-numbered carbon atom in the ring is exoplanar (examples 5 and 6). Boats. The reference plane is defined by the two parallel 'sides' of the boat (eltamples 7 and 8). Skews. Each skew form has two potential reference planes. containing three adjacent atoms and the remaining non-adjacent atom. The reference plane is so chosen that the lowest -numbered carbon atom in the ring. or the alom numbered next above it, is exoplanar. in that order of preference (examples 9 and 10). Half-ehnirs. The reference plane is defined by the four adjacent coplanar atoms (example 11). Envelopes. The reference plane is defined by the five adjacent coplanar atoms (eumple 12). Five-membered rings Envelopes. The reference plane is defined by the four adjacent coplanar atoms (examples 1 and 2). Twists. The reference plane is defined by three adjacent ring-atoms, so chosen that the exoplanar atoms lie on opposite sides of the plane (examples 3 and 4). Note 1. Many of the possible conformations are not likely to cootribute significantly to the chemistry of a particular monosaccharide, but must be stabilized by formation of additional rings, as in anhydrides or other derivatives. Some others may occur as InII1sition-state intermediates. Note 2. A more precise specifICation ofconformation can be achieved by use of the Cremer-Pople puckering parameters [22]. 2-Carb·7.4. Eoantiomers The conformational symbols for enantiomers are different It is therefore important to state in the context whether the 0 or the L form is under consideration. Enantiomers have the same reference plane (see 2-Carb-7.3), and it should be noted that the mirror image ofa-D-glucose-4C\ is a-L-glucose-1C4.

HO~~' H~H H OH

L-/ ___mirror plane --' / ~HO OH HO ' OH OH H H

Mirror images: a-o-glucopyranose-"e1 (upper) and a-l-g1ucopyranose- 1 C4 (lower) 2·Qub.8. Aldoses 2-Carb-8.1. Trivial names The ai

The configuration of the CHOH groups of the sugar is designated by the appropriate configurational prefix(es) from Chart L When used in systematic names, these prefIXes are always to be in lower case letters (with no initial capital), and italicized in print. Each prefix is qualified by 0 or L (Chart I shows only the 0 structures). Examples; o-riI»PentO$e lor o-ribose o-manno-HexO$e lor o-mannose. The trivial names are preferred for the parent sugars and for those derivatives where all stereocenlres are unmodified. 2-Carb-8.3. Multiple configurational prerlXes An aldose containing more than four cbiraI centres is named by adding two or more configurational prefixes to the stem name. PrefIXes are assigned in order to the chiral centres in groups of four. beginning with the group proximal to C-l. The prefix relating to the group of carbon atom(s) farthest from C-I (which may contain less than four atoms) is cited first. Examples;

HC=O I HOCH I HOCH I HCOH I HCOH I HOCH I HOCH I HOCH, CH"OH

o-glycero-D~Heptose l-ril»o-manno-Nonose not o-gluco-o-gJycero-heplose not o-manlJOoL -nbo-nonose 2-Carb-S.4. Multiple sets oC chiral centres If sequences of chiral centres are separated by non-chiral centres, the non-chiral centres are ignored. and the remaining set of chiral centres is assigned the appropriate configurational prefix (for four centres or less) or prefixes (for more than four centres)_ Example: CHO I HCOH, ?Ho HCOH, HCOH I ~ HOCH I HCOH I HOCH I CHptl

3.6-DideoXY-L-tMJo.l·tlfIo.decose Note 1. This convention is not needed for parent aldoses. only for deoxy aldoses. ketoses and similar compounds (see 2-Carb-l0.4 and 2-Carb-ll.2). Note 2. Since all a1doses up to the have trivial names that are preferred, the systematic names apply only to the higher a1doses. However. the configurational prefixes are also used to name ketoses (see below) and other monosac­ charides. 2.Carb-8.5. Anomeric configuration in cyclic forms

For the specification of !l and p in cyclic forms see 2-Carb-6. 2778

2-Carb-9. Dialdoses Systematic names for individual dialdoses are formed from the systematic stem name for the corresponding aldose (see 2-Carb-8.2), but with the ending 'odialdose' instead of 'ose', and the appropriate configurational prefix (Olart f). A choice between the two possible aldose parent names is made on the basis of2-Carb-2.2.2. EKamples:

CHO I HCOH I CHO HOCH I I HCOH HOCH I I HOCH HCOH I I CHO CHO

l·threo-Telrodialdose galacto-Hexodialdose Note. lbe prefix 'muo·' could be included in the latter case, but it is not needed to derme the slructure. If a cyclic form is to be named, the locants of the anorneric centre and of the carbon atom bearing the ring oxygen atom must be given (in that order) (cf. 2-Carb-6.4). If there is more than one ring size designator, they are placed in alphabetical order (e.g. furanose before pyranose). Examples:

CHO HOT;id.CHO HO~ OH OH OH OH

a;.o·gJuco+Iexodiaklo-1.5·pyranose (6R)-o-gfuco-Hexodialdo-6,2'pyranose

OH~ OH Methyl a;-o-gIuccH1exoal3ldo-6.3-furanose-1 ,5-pyranoside 2-CarlJ-IO. Ketoses 2-Carb-lO.l. Classification Ketoses are classified as 2-ketoses. 3-ketoses. etc.• according to the position of the (potential) carbonyl group. The locant 2 may be omitted if no ambiguity can arise, especially in a biochemical context. 2-Carb-lO.2. Trivial names Ketoses with three to six carbon atoms are shown in Olart IV, with trivial names (and three-letter abbrevia­ tions) in parentheses. (See also the alpbabeticallisting of trivial names in the Appendix.) The trivial names 'Ikrythrulosc' for o-glycero-tetruJose, 'o-' for D-eryrhro-pent-2-ulose. and 'o-xyl­ ulose' for o-rhreo-pent-2-ulose contain stereochemical redundanCy and should not be used for naming derivatives. is the accepted trivial name for I>-altro-hept-2-ulose. 2-Carb-lO.3. Systematic names The systematic names are formed from the stern name and the appropriate configurational prefix. The stem names are formed from the corresponding aldose stem names (2-Ca.rb-S.2) by replacing the ending '-ose' with' -ulosc'. preceded by the locant of the carbonyl group, e.g. hex-3-ulose. The chain is numbered so that the carbonyl group receives the lowest possible locant If the carbonyl group is in the middle of a chain with an odd number of carbon atoms, a choice between alternative names is made according to 2-Carb-2.2.2. 2779

Note. In Chemical Abstracts Service (CAS) usage the Iocant for !be c:arbonyl group precedes the stem name, c.g. 3-hexulose. For examples sec 2-Carb-lO.4.

crHPi c=o CHPi 1. l-DIIydroxyacetone crHPi cr=o ~ cHpi o-g/yceto-TeIIuIose CO-EIyI/InJIose") YHzOH YHzOH C=O I c=oI HYOH HO?l HCOH ~ Ctipl CIftOH ~-2-uIose o-/IIt8o-PeIJI.2-u1oH ('D-RIbuIose.; o-Rul) Co-': o-XuI)

yHzOH yHzOH YHzOH YHzOH C=O C=O C=o C=o I HOCH ttCoHI Hoe..I ttCottI HCOH HCOH HOCH HoCH I , , H«OH HOOH, HCOH, H¢oH CHzOH CHzOH CHzOH CHzOH O·lIIo-Hex-2-u1ose o-aflll>lno.Hex-2-ulose o-JI)'Io-Helt-2-<11ase o-lyxo-Hex-2-<11ase (D-Pslcose; o-Pso) (o-FrucIOSe; D-Fru) (O-SoIboSe; D-Sor) (0-; 0-Tag)

Chart IV. StruCtures, with systematic and trivial names. of the 2-k.ctoscs with three to six carbon atoms 2-Carb-lO.4. Coafigurational prefaal For 2-kctoscs, configurational prefixes are given in the same way as for aldoses (sec 2-Carb-S.2 and 2-Carb-8.3). ExafI1:IIes: ?HPi c::o ~H I C=O HOCH I I HOCH HCOH HO~\ I I y--y~OH HCOH HCOH I I HOCH HCOH OH OH I I CHzOH CHzOH L-xyto.Hex-2-u1ose o-aJtro.Hept-2-uIose (L-50lbose) (O-Sedoheptulose)

rH~ C::O I HOCH I HOCH I HCOH I HCOH I HOCH I CH~

L-gi)qro-o-manno

For ketoses with the carbonyl group at C-3 or a higher-numbered caIbon atom. the carbonyl group is ignored and the set of chiral centres is given the appropriate prefix or prefixes according to Clart I (cf 2-Carb-S.4). Examples: 9HzOH yHzOH HOCH hept-4-ulose

H~}c=oI H~ D·.' L.fI/UCo- HCOH fc=o } I I HCOH HOCH I H~ } l-el)'lllm- j: }L-u.wo. HOCH I I CI¥>H Ct¥>H L-thIBO-D-BIIo-Non-3-ulose L-Bl)'thnH.-gluco-Non·5-ulose not D-"'reo-o-sllo-non·5-ulose 2-Carb-ll. DiJcetoses 2-Carb·l1.l. Systematic names The systematic name of adiketose is formed by replacing tile terminal '·se' of tile stem name by '-diulose'. The looants of the (potential) caIbonyl groups must be tile lowest possible and appear before the ending. The stem name is preceded by the appropriate configurational prefix_ If there is a choice of names, a decision is made on the basis of 2·Carb-2.2.2. In cyclic forms, locants may be needed for the positions of ring closure; that of the (potential) carbonyl group is cited first. Examples: ~~ fl¥)H c=o, c=o HCOH I I HCOH HOCH I I HOCH HCOH c=oI c=oI , I CHzOH CHzOH L-~,s.diulose meso-xyto-Heplo-2,6-diulose 2-Carb·ll.1. Multiple sets of cbiral centres If tile carbonyl group(s) divides the sequence of chiral centres, the configurational prefixes are assigned in the normalllUlllllCl" (see 2-Carb-8.4) for all chira! centres; the non-chiral centres are ignored. Examples: '(HzOH HCOH, '(HzOH HOCH c=o c=oI I I HOCH C=O I H~06iJI¥)H I c=o HOCH I I HCOH ~>---r6H I o H HO

~OH C=O ~)D-manno- $}" .... HCOH C=O I I C=O HCOH HatH Il-g¥:e/O- Htoo I D-glycero- I I C~ ~ L-g/ycetoi>-lll8IlIIO-Nono-2.7 -diulose o-gIycero-O-ido-Hono-3.&diulose 2-Cmb-12. Ketoa1doses (aldolcetoses, aldosuloses) 2-Carb-12.1. Systematic names Names ofketoaldoses are fonned in the same way as those of diketoses. but with use of the tennination '-ulose' in plareofthetenninal'-e' of the corresponding aldose name (2-Oub-8.2). The carbon atom of the (potential) aldehydic carbonyl group is numbered 1. and this locant is not ciled in the name. The locant of the (potential) ketonic carbonyl group is given (as an infix bef~ '-ulose') unless it is 2; it may then be omitted (in this text, this locant is always tetained for the sake of clarity). In cyclic fonns,locants may be needed for the positions of ring closure; that of the (potential) carbonyl group is cited first The position of the ring-size designator (e.g. pyrano) depends upon which carbonyl group is involved in ring formation (see examples). Examples:

CHO I HOCH I HCOH c=o MeOfH~I I HOCH HCOH I I c=o HCOH I I HCO CH~H I CH,OH

o-smbirnrHexos-3-ulose Methyt Ji-o-~hexopyranosid-4·ulose

eOf- CHO HOCH H~OOMe [jI H OH HCOH I HOCH2 CHO DC I OH H CHzOH

2-Carb-12.2. 'Debydro' names In a biochemical context, the naming of a1doketoses as 'dehydro' a1doses is widespread. Thus o-xyio­ hexopyran0s-4-ulose would be termed 4-dehydro-D-glucose. This usage of 'debydro' can give rise to names which are stereochemically redundant, and should not be employed for naming derivatives. Note. In Enzyme Nomenclature [23J dehydro names are used in the context of enz.ymic reactions. The substJ:ate is regarded as the parent compound, but the name of the product is chosen IICCOrding to the priority given in 2-CaJb. 2.2. Examples: o-GJucose + Oz '" 2-dehydro-o-gJucose + H202 (Be 1.1.3.IO)

Sucrose + acceptor = ~o-fructot"unnosyl 3-dehydro-a.().allopyranoside + reduced acceplor (EC 1.1.99.13) L- + NADP~ " S-dehydro-D-fiuclose + NADPH (reaction or sorbose dehydrogenase, EC 1.1.1.123) 2782

2-Carb-13. Deoxy sugars 2-Carb-13.1. Trivial names Several deoxy sugars have trivial names established by long usage, e.g. (Fuc), quinovose (Qui) and (Rha). They are illustrated here in the pyranose fonn. These names are retained for the unmodified sugars, but systematic names are usually preferred for the fonnation of names of derivatives, especially where deoxygenation is at a chiral centre of the parent sugar. (See also the alphabetical listing of trivial names in the Appendix.) Examples:

c~ 0 HO~OH ~C""--o-l°H HO-.£...;!;-( OH OH OH

a-l·Fucopyranose ~-D.QuinoYOpylllnose L-Rhamnopyranose 6-Oeoxy-a-l-galactopyranose 6·Deoxy-jH!-g/ucopyl'anose 6-Deoxy-l-mannopyranose

HO~OH OH 2,6-Dideoxy-/H>-ribcHlexopyranoSB

(~-Digiloxopyranose)

HO 0 ~q HO~C~OH ~OH OH OH

3.6-Dideoxy-JH>-xyicHlBXopyranosB 3,6-Dideoxy-ll-o-atlilbino-he"opyranose (JI-Abequopyranose) (IHyvek)pyranose) Other lrivial names that have been used include ascarylose for 3,6-dideoxy-L-arobino-hexose, colitose for 3,6-dideoxy-L-.qlo-hexose and paratose for 3,6-dideoxY-D-ribo-hexose.

Note.SugatS with a terminal CH] group shouldbenamcd as m-deoxy sugars, as shown above, nOl C-medtylderivatives. 2-Carb-13.2. Names derived from trivial names of sugars Use of 'deoxy-' in combination with an established lrivial name (see Ouuts I and U) is straightforward if the formal deoxygenation does not affect the configuration at any asymmetriceentre. However if 'deoxy' removes a cenlIc of chirality, the resulting names contain stereochemical redundancy. In such cases, systematic names are prefetred. especially for the naming of deri valives. Note. The names 2- (for 2-deoxy·lHrythro-pentose) and 2-deoxygIucose (for 2-deoxy-O-iJrabiM-hexose) are often used.

O~2- I CHz 0 ~H'OH

HO H

2-Deoxy.o-el}'tlw-pentofuranose 5-phosphate 2-Carb-13.3_ Systematic names The systematic name consists of the prefix 'deoxy-'. preceded by the locant and followed by the stem name with such configurational prefixes as necessary to describe the configuration(s) at the asymmetric eentres 2783

present in the deoxy compound. Configurational prefixes ~ cited in order commencing at the end farthest from C-I. 'Deoxy' is reg8Idcd as adctachable prefix, i.e. it is placed in alphabetical order with any substituent prefixes. Note. The treatment of 'an hydro' (see 2-Carb-26), 'dehydro' (see 2-Carb-17 .3) and 'deoxy' as detachable preflXCS follows long-standing pr'ICIicc in carbohydnre chemistry, but is in conflict willi [14] (p. 12). Examples: CHO I HCH I HCOH I HCOH I HCOH I CHzOH 2-0e0xy-o-lIbo-hexose not 2.

3 c=o?H I HOCH I ~ Ii HCOH I HCOH I HOCH I CHzOH

2-Deoxy-a-o-al1o-heptopyranose

Methyl 3-azido-4·Obenzoyl-6-bromo-2,3,6-trideoxy-2..fJuoro-a-o-allopyranoside If the CH2 group divides the chiral centres into two sets, it is ignored for the purpose of assigning a configurational prefix; the prefix(es) assigned should cover the entire sequence of chiral centres (sec 2-Carb-S.4). Examples: «HzOH CtiO HOCH I I HCOH c=o I I HCOH ?Hz I HCOH I ?iz HCOH HOOH I I CHzOH CHpi 5-Deoxy-o-atabfno.hept-3-u1ose not 5-deoxy-o-g/)ceto-o-gl)':erc>-t. -~ro-hept-3-u1ose

c=o?'izOH I ~ HCOH I HOCH I ~ HOCH I CHzOH 6-Deoxy-t. -gfuco.oct-2-ulose not 6-deoxy-L-gI}ouD-t.-~-2-ulose 2784

If the anomeric hydroxy group is replaced by a hydrogen atom, the compound is named as an anbydro alditol (2-Cacb-26). 2-Carb-13,4. Deoxy alditols The name of an aldose derivative in which the aldehyde group has been replaced by a terminal CH3 group is derived from that of the appropriate alditol (see 2-Carb-19) by use of the prefix 'deoxy-'. Examples:

H3 9H~ CH20H 1 9 I ~ HOCH HOCH HOCH HOCH I I I I HCOH HOCH HCOH E HOCH I I I I HCOH HCOH HCOH HCOH I I I I CH~ 5 CH3 CH3 CH~

1-Deoxy-o-arablnitol 5-Deoxy-o-arabinitol not 5-deoxy-o-Iyxflol not 1-deoxy·o-lyxitol The a1ditols from fucose and mamnose are frequently termed fucitol and rlIamnilol (see 2-Carb-19.). 2-Carb·14. Amino sugars 2-Carb-14.1. General principles The replacement of an alcoholic hydroxy group of a monosaccharide or monosaccharide derivative by an amino group is envisaged as substitution of the appropriate hydrogen atom of the corresponding deoxy monosaccharide by the amino group. The stereochemistry at the carbon atom carrying the amino group is expressed according to 2-Carb·8.2, with the amino group regarded as equivalent to OH. Some examples of N-substituted derivatives are given here; for a detailed treatment see 2-Carb-2S. 2-Carb-14.2. Trivial names Accepted trivial names are as follows. D-Galactosamine for 2-amino-2-deoxy-D- D-Glucosamine for 2-amino-2-deoxy-o-glucose D-Mannosamine for 2-amino-2-deoxY-D-mannose D-Fucosamine for 2-amino-2,6-dideoxY-D-galactose D-Quinovosamine for 2-amino-2,6-dideoxY·D-glucose for 5-amino-3.5-dideoxY-D-glycero-o-galacto-non-2-ulosonic acid Muramic acid for 2-amino-3-0-[(R)-1-carboxyethyl]-2-deoxy-D-glucose. In the last two cases the trivial name refers specifical1y to the D enantiomer. (See also the a1phabeticaJlisting of trivial names in the Appendix.) Such names as 'bacillosamine' for 2,4-diamino-2,4,6-trideoxy-D-gJucose and 'garosamine' for 3-deoxy-4-C­ methyl-3-methyJarnino-L-arabinose are not recommended, as they imply replacement of OH by NH2 in a nonexistent parent sugar. Examples:

Cl:f20Ho OOH~ NH.OH

2-Amino-2-deoxy·o-gIucopyranose (o-glucosanlne). 2785

H -rOH rH2 OH C]HCOH, AcNHCH, OCH HOC~O-r: relerence HC' OH AcN:~ atom - , OH HCOH, CH,OH OH H 5-Acetamido-3,5-dideoxy-o-glpro-a-o-gaJacto-non-2-ulopyranosonic acid (N-acetyl-a-neuraminic acid, a-NeuSAc), drawn in three ways (note that C-7 is the anomeric reference atom)

CH20H o

H NH2

2-Amino-3-0{(R)·1-<:arboxyethylJ-2-deoxy-/l-o-glucopyranose (li-muramic acid) For examples with nitrogen in the ring, see 2-Carb-34.L 2-Carb-14.3. Systematic names The compounds are named by use of a combination of 'deoxy-' and 'amino--' prefixes. When the complete name of the derivative includes other prefixes, 'deoxy-' takes its place in the alphabetical order of detachable prefixes. Examples: OH HOCH2--r---o-----7' Ho~NHMe OH

2-Deoxy·2-methylamill

CH3 OHCNH~OOMe MeO OH

4,6-Dldeoxy-4-formamido-2,3-di-Omethyl­ 2-Acetamido-l,3,4-tri-G-acetyl-2,6-dideoxy­ o-mannopyranose a-L -gaIactopyranose When the amino group is at the anomeric position, the compound is normally named as a glycosylamine (see 2-Carb-33.6). 2-Carb-lS. Thio sugars and olher eha/cogen analogues Replacement of a hydroxy oxygen atom of an aldose or ketose. or of the oxygen atom of the carbonyl group of the acyclic fonn of an aldose or ketose. by is indicated by placing the prefix 'thio'. preceded by the appropriate loean!, before the systematic or trivial name of the aldose or ketose. Replacement of the ring oxygen atom of the cyclic fonn of an aldose or ketose by sulfur is indicated in the same way, the number of the non-anomeric adjacent carbon atom of the ring being used as loeant. and compounds are named likewise, by use of the prefix 'seleno' or 'teHuro·. Sulfoxides (or selenoxides or telluroxides) and sulfones (or selenones or tellurones) may be named by functional class nomenclature [13]. 2786

Note. 1be appropriate prefIX is Ibio. not Ibia; the latter is used in systematic organic to indicate replacement ofCH2 by S. Examples;

Cti20~ CI:i2QH S AcO~SH HO~OH OAc OH

2,3.4,6-Tetra-o-acelyl-1-thi()-~-o-glucopyranose 5-Thlo-~-o-glucopyranose r- HCOMe H HOCH:.~SeOH H H?OH AcOCH~Q0': HOCH J .. I H OMe " HCOAc I I H OH HCSe HCO I I CH,OH cH,OTr Methyl 2,3,4-tri-o-acelyl-1·thi0-6-O-trilyl-a-o-glucopyranoside Methyl 4-seteno-a-o·xylofuranoside

H~Q HO~OH OH

4-Thio-~alactopyranose a-o-Glucopyranosyl phenyl (R)-selenoxide

ytl, HOCH:z-CO~Me HCCAe HOC!WCH,OH HOCH I HHO E I AcOCH H«SE~.I HCOH H 0Me I HCS HOSe I HO H I HCOAc CH:OH I CH~ Methyl 5·seIeno-«-o..fructofuranoside Ethyl 3,4,6,7-tetra-o-acetyl-2-deoxy-l ,5-dilhio-a·o· g/uco-heplopyranoside Note. It is common practice in carbohydrate names to regard 'thio' as detachable. and therefore alphabetized with any other prefixes. 2-Carb-16. Other substiluud monosaccharides 2-Carb-16.L Replacement of hydrogen at a non-tenninal carbon atom. The compound is named as a C-substituted monosaccharide. The group having priority according to the Sequence Rule

AcO~COOH0 AcO Br AtiO CAe (5R)-1,2.3,4-Telra-D-acelyl-5-brorno-a-o-xyfo-hexopyranuronlc acid or 1.2,3,4-tetra·o-acelyl-5-brorno-fH. -idopyranuronic acid 2787

2-Carb-16.2. Replacement of OB at a non-tenninal, non-anomeric carbon atom The compound is named as a substituted derivative of a . The group replacing OH detenn.ines the configurational description. Any potential ambiguity should be dealt with by the alternative use of the R,S system to specify the modified stereocentre. Examples:

CHoOH HO~ PI'I OH

2-Deoxy-2-phenyl-a-o-gluoopyranose or 2-deoxy-2-C-phenyl-a.o-glucopyranose or (2R)-2-deoxy·2·phenyl-o:-D-arabi~hexopyranose

2,3-DIazido-4-O-benzoyl-6-bromo-2.3,6-trideoxy-a-D-mannopyranosyi nitrate Note. Use orlbe symbol C- is essential only in cases of potential ambiguity, to make clear thai substitution is aI carbon rather than at a heteroatom (cC. 2-Carb-1B.2); however, it may also be wed for emphasis. 2-Carb-16.3. Unequal substitution at a non-tenniDal carbon atom The compound is named as a disubstituted deoxy sugar. Configuration is determined by regarding the substituent having priority according to the Sequence Rule ([l3). Section E). as equivalent to OH. Any potential ambiguity should be dealt with by the alternative use of the R,S system to specify the modified stereocentre. Example:

H~

OH

(2FQ-2-Bromo-2-chloto-2-deoxy-«-o-arabinc>-hexose or 2-bromo-2-ch1oro-2-deoxy-a-D-gIucopyranose (Br has priority over CI) 2-Carb-16.4. Terminal substitution If substitution at the terminal carbon atom ofthe carbobydrate chain creates a chiral centre, the stereochemistry is indicated by the R,S system. Example:

CHO HCOH• J HOCH HfOHI O COH J Ph

(5R)-5-C-Cyclohexyl-5-G-phenyl-o-xy\ose Note. A monosaccharide with a tenninaI methyl group is named as a deoxy sugar, nol as a C-rnethyl derivative.

Substitution of aldehydic H by a ring Of ring system is indicated simply with a C-substiluent prefix. 2788

Exampfes:

Ph I c=o I HCOH I HO~C\¥)H0 HOCH I HO OH HCOH OH I HCOH Ph I CH,OH l-C-Phenyt·o-glucose 1·C-Pheny!·p·o-glucopyranose not l-C-phenyt·o-gluco-hex·l-ulose 2-Carb-16.5. Replacement of carbonyl oxygen by nitrogen (imines, oximes, hydrazones, osazones etc.) The imino analogue of a monosaccharide may be named as an imino-substituted deoxy alditol. Example: CH=NMe I HCOH I HOCH I HCOH I CJ¥)H l-Deoxy-l-(methylimino)-o-xytitol Oximes. hydrazones and analogues are named directly as oxime or hydrazone derivatives etc. Exarr.,le: CH=N-NHPh I HCOH I HOCH I HCOH I HCOH I CH:!OH o-Glucose phenylhydrazone The vicinal dihydrazones formed from monosaccharides with arylhydrazines have been called arylosazones. but are preferably named as ketoaldose bis(phenyJhydrazone)s Example: CH=N-NHPh I CH=N-NHPh I HOCH I HCOH I HCOH I CHzOH o-stabino-Hexos-2-u1ose bis(phenythydrazone) or o-sllJblno.hex·2-ulose phenylosazone The triazoles formed on oxidising arylosazones (commonly called osotriazoles) may also be named as triazolylaJditols. HC?I, I NPh ?"'N' HOCH I HCOH I HCOH I CH:!OH

D-smbino-Hexos-2-ulqse phenyIosotriazoe or (1 RH -(2-phenyt-2H-l,2,3-triazo1-4-y1)-o-el)'lhritol or 2-phenyt-4-(O-ambiJ1o.1,2,3,4-telrahydroxybutyf)·2H-l ,2,3·triazole 2789

2-Carb-16.6. Isotopic substitution and isotopic labelling Rules for designating isotopic substitution and labelling are given in [13] (Section H). Parentheses indicate substitution; square brackets indicate labelling. The locant U indicates uniform labelling. Examples: 0-(1-'3C)Glucose (substitution) 0-(2-2H)Mannose (substitution) L-IU)4C)Arabinose Oabelling) o-[l-3HIGalactose (labelling) When isotopic substitution creates a centre of chirality, configuration is defined as for other types of substitution (see 2-Carb-16.1 to 2-Carb-16.4). Example: CHO 2Hd.t I HOCH HO~ I HfOH HO ,~ OH c~ 2-DeoXY.0-(2-2ti)lyxose (substituted) 2-DeoXY-2-(18F)f1UOFs;D-QIUCOSe (labened) or (2S)-2-deoxy-o-threo-(2-2H)pentose or (2R)-2-deoxy-2-{ 8F]fluoro-o-al3bino-hexose 2-Carb-17. Unsaturated monosaccharides* 2-Carb-17.1. General principles This section relates to the introduction of a double or triple bond between two contiguous carbon atoms of the backbone chain of a monosaccharide derivative. A double bond between a carbon atom of the backbone chain and an atom outside that chain, or a double Or triple bond between two carbon atoms outside the backbone chain, will be treated according to the normal rules of organic nomenclature [13,14J. 2-Carb-17.2. Double bonds Monosaccharide derivatives having a double bond between two contiguous carbon atoms of the backbone chain are named by inserting. into the name for the corresponding fully saturated derivative. the infix 'x-en'. The infix is placed directly after the stem name that designates the chain length of the sugar. The locant x is the lower-numbered carbon atom involved in the double bond. Steric relations at a double bond are designated, if necessary, by the standard stereosymbols '(Z)-' and '(E)-' preceding the whole name ([13], Section E). For multiple double bonds, infixes such as 'x,y-dien' are used (preceded by an inserted 'a' for euphony). Note 1. 'The term 'glyeal' is a non-preferred, trivial name for cyclic enol ether derivatives of sugars having a double bond between carbon atoms I and 2 of the ring. [t should not be used or modified as a class name for monosaccharide derivatives having a double bond in any other position. Note 2. Following the principle of first nanilitg the saturated derivative, compounds having a C=CR-Q- group as part of a ring system are named as unsaturated derivatives of anhydro alditols if R is hydrogen ()(' carbon; if R is a , cbalcogen. or nitrogen-family element, the resulting name is that of a glycenose or glycenosyl derivative. Note 3. 'The symbols (Z)- and (E)- may be omitted when the double bond is located within a ring system of six atoms or less. as steric constraints in such systems normally pennit only one fonn. Exampfes:

1.5-Anhydro-2-deoxy-D·al3bino-hex-1-enitol (nonlIreferred triviat name o-glucal)

This is based on the 1980 recommendations [5J. Some examples have been omitted. 2790

o H HOCH 0 j-N «~ ~p(=O H H H H H H Methyl 2-deoxy-o-threo-pent-1-enofuranoside 1-(2-0eoxy-o-thrso-pent-l-enofuranosyl)uracil

Ad)~ ~o Ad) H 3,4-Di-O-acetyt-2-deoxy-o-el)lfh/TJ1lllnt-1-enopyranosyt chloride

HO~-~r% OH H 2,6-Anhydro-1-<1eoxy-o-aItro-hept-1-enitoi (alphabetic preference over 2,6-anhydro-7-<1eoxy-o-talcHlept-6-enilol) ~ OAe CH I I H~C':-C~OAe HOCH I I HCOH HCOAc I I HCOH HCOAc I I C~OH ct¥)Ac 1,2-Dideoxy-o-atabino-hex-l-enitol (2)-1,2,3,4,5-Penla-O-acetyl-D-etythro-pent-1-enllol

H I MeO'C~oMe 11 AcO~C,:-C~OAc CH I I HCOAe HOCH I I HCOk HCOH I I ~Ae C~H

(E)-1 ,2,3,4,S-Penla-O-acetyl-o-etyt/ln:).pent-1-enitol 2-0e0xy-o-threo-pent-l-enose dimelhyt acetal

~H2 CH I HOCH I CH II CH I HCOH I HCOH I cHzOH

2,3-Dideoxy-a-o-ef}'thro-hex-2-enopyranose 1,2,4,5-Tetradeoxy-o-anlbin(){)C\a-1,4-dieniloi HU-r°\!/ HO OH l,5-Anhydr0-4-deolCf-o-erythro-hex-4-enltol (enantiomeric precedence over 2,6-anhydro-3-deolCf-L-erythro-hex-2-enitol) 2791

H v!-0\iOMe H~~H H H Methyl 3.4-dideoXY*D-gl)cem-hex-3-en-2-ulopyranoside

CH,OHo H o H =OOH H H

2,3-Dideoxy-a-o-gIycM>-hex-2-enopyranos-4-ulose ~O;;OMe o {).H ct¥)H H H Methyl 3,4-<1ideoXY-P-D-g/}'cero-hept-3-en-2-ulopyranosid-5-ulose

OH H,C~ OH

H O-CMe2\

5-Deoxy-l ,2-O-isopropylidene-jH. -th~nt-4-enofuranose

CH2 Hb' 0 H QOH I 0 \ H O-CMil2

5,6-Dideoxy-l,2-0-is0propyliderKHx-o-xyfo-hex-5-enoIuranose 2·Carb·17.3. Triple bonds and cumulative double bonds Monosaccharide derivatives having a triple bond or cumulative double bonds in the backbone chain are named by the methods of 2-Carb-17.2, with the infix 'n-yn' for a triple bond and infixes such as 'ij-dien' for cumulative double bonds. Note. This approach was not included in [5]. Alternatively they can be named on the basis of the corresponding fully saturated sugar by using the appropriate number of dehydro and deoxy prefixes (deoxy operations are regarded as formally preceding dehydro operations). The prefixes are placed in alphabetical order before the stem name.

Exa~s:

(2)-1,7 -Anhydm-2,5,6-trideoXY-D-xyIo-oct-5-en-l-ynitol or (2)-1 ,7 -anhydro-l,I,2.2-tetradehydro·2.5,6-lrideoxy-o·xyfo-oct-5-enitol 2792

OMe I C III C I HOCH I HCOH I CHzOH 2-Deoxy-1-o.methyl-o-thl8O-pent-1-ynito1 or 1,1.2,2-tetradehydro-2-<1eoxy-1-Q-methyl-o-tIwo-pentitol

c,9H> . " " o H)-o\ .. O I Me,C,=>-< .... O 'o,CMe:!

6,7,8-T rideoxy-1 ,2:3,4-di-o.isoPfOllYlide~-D-gafacto.octa-6,7-dienopylanose or 6,7 ,7 .8-tetradehydr0-6,7,8-lrideoxy-1,2:3,4-di-o.isopropyllde~-o-ga/aCfo.octopyranose 0Ac, C III

~H OH 6-O-Acetyl-5-deoxy-«-o-~-5-ynofuranose or 6-Q.aceIyI-5,5,6,6-tetradehydro-5-<1eoxy-«-o-xyto.hexo/uranose

'~B0 H OH H o \ H o-CUe:! 5,6,1HrIcIeoxy-1,2-D-isopropyIiden!Hx-o-xyto.oct-5-ynofuranos-7 -ulose or S,s,6,6-Ie1radehydro-S,6,8-trideoxy-1,2-Q.isopropy1ida-o-xyto.octofuranos-7-u1ose 2·Club-IB. B1'dtU:W-c1ulin sugars· 2-Carb-lS.l. TriftalllllllU!S Several branched monosarobarides have trivial names, some established by long usage. Examples are given below, together with systematic names for the (cyclic or acyclic) forms illllS1ratcd. (See also the a1pbabetical listing of trivial names in the Appendix.) Enaotiomers of the sugars listed should be named systemalically. Examples: ~~" Ott Ott Hamamelose 2-C-(Hydro~o-ribopyranose

This is a modified form of the 1980 recommendations [4]. Priority is now given to naming cyclic foons. sioce in most cases branc:hed-chain monosaccharides will fonn cyclic bemiacetaIs or bemiketaIs. 2793

CH,-;;;,;o-o-lOH HO~ CH. Cladinose 2.6-Oideoxy-3-G-methyl-3-Q.meIhyl-l-ribo-hexopyranose

~O~H'OH Hi 'f---Y" I OH OH

Streptose S-Oeoxy-3-G-formyl-L-lyxofuranose

0 HO~Ct13OH HO CHo OH

6-Deoxy-3-G-methyt-o-mannopyranose (Evalose)

C~OH3 H C 0 Mea 3

O~

2,3,6-Trideoxy-3-C-methyl-4-().methyl-3-nltl'O-L-ambino-hexopyranose (Evemitrose) MeLo, MeNH~ OH OH

3-Deoxy-4-C-melhyl-3-methyfamino-L-arabinopyranose (Garosamine)

CHO I HCOH I HOCH,-y-CHzOH OH

o-Apiose (Api) 3-G-(Hydroxymethyl)-o-glycero-tetrose Note_ For the cyclic forms of apiose, systematic names ate preferred, e.g.

o H ~c~ H OH HO OH

3-C-(Hydroxymethyt)-a-o-elYlhrofuranose [The name a-D-erythw-spiofuranose is ambiguous; Chemical Abstracts Service (CAS) uses the trivial name o-apio­ a-D-furanose; Beilstein gives (3R)o(l-o-apiofu~nose) 2794

2-Carb-18.2. Systematic names A branched-chain monosaccharide is named as a substituted parent unbranched monosaccharide. as outlined in 2-Carb-16.1 to 2-Carb-16.4. Note. C-Locants are essential only where there is potential ambiguity, to make clear whether substitution is at carbon or at a heteroatom (cf. 2-Carb-16); however, they may also be used for emphasis. 2-Carb-18.3. Choice of parent If the branched monosaccharide fonns a cyclic hemiacetal or hemiketal, the chain which includes the ring atoms rather than any alternative open chain must be the basis of the name. Otherwise the parent is chosen according to the principles given in 2-Carb-2.1. Examples (see also Chart V):

CHO CHO . 1 I HCOH HCOH 1 1 H

CHO 1 ~ <>.N-y-CH. MeOCH 1 HCOH I CH3 2.3,6-Trideoxy·3-C-methyl-4-O-methyl-3-nitro-o-lyxo-hexopyranose (nitrogen has priority over carbon for detennining configuralion)

CHO I HCOH I O?-CH,OHHCOH HCOH I CH.oH 4-Cyclohexyl-4-deoxy-4·(hydroxymethyf)-o-allose [oxygen (in CH20H) has priority over carbon (in cycIohexyf) al C-4) or (4R)-4-cyclohexyl-4-deoxy-4-(hydroxymethyl)-o-JiOO.hexose If the two substituents at the branch point are identical. so that this centre has become achiral, the stereochemistry is specified as described in 2-Carb-S.4.

Exa~es:

CHO I HCOH CHO I I ~qCH3 HCOH I HCOH I ~ HCOH HOCHo-y-CHoOH I CHoOH OH

3-Deoxy-3,3-dimelhyl-o-JiOO.hexose 4-G-(Hydroxyrnelhyl)-o-erythro-pentose Note. Cyclization of the second example between C-I and a CH20H group would necessitate a three-cenll'e configu­ rational preilX for the ring fann. 2795

C~OH 1 HOCH 'CHO .t HOCH 31 OH HO~ ~~"OH '!TOH 1,H HC-C' I sl \. ... OH HOCH H HCOH C···H I I '.-OH HCOH CHO "C"'H I CHO ~ 2

7 'COO C~OH 2i 61 HCOH HOCH 0 31 HCOH S~H OH.CHzOH OH H 3 • I t .... H I HC-C, OH HOCH OH sf C..... I HOCH ' ..... H HOCH ~==OC~OH I CHO 7~

3 4 CHO CHO I I HCOH HOS 'f'H I C-COH HC-C~-CH-~OH I I I I ~C-CH ~OH CH3 C~ I I HOCH HCOH I I CH,OH CH, 5 6

1 3-Deoxy·3-[( I R.2S)-I,2-dihydroxy-3-0xopropyl)-D-,lyaro-o-altro-heplopyrancse or 3-deoxy-3-{IHhreo-l,2-dihydroxy-3-oxopropyl}-D-glyaro-o-a/tro-heptopyranose (DOt the alternative open-dlain siJ<-carbon dialdose or eight-carbon aldose. ct. 2) 2 4-Deoxy-4-

2-Carb-18.4. Naming the branches Each branch will be named as an alkyl or substituted alkyl group replacing a hydrogen atom at the branch point of the parent chain. Within the branches, configurations around asymmetric centres can either be indicated using the R,S-system or, if they are carbohydrate-like and assignment is straightforward, by the use of the configurational prefix. For this purpose, and in the absence of a carbonyl group (or a terminal COOH or its equivalent) in the branch, the point of attachment of the branch (on the main chain) is regarded as equivalent to an aldehyde group. Example:

I HOCH I HCOH I HOCH I HOCH I CH,oH

l-gIucxr l,2,3,4,5-Pentahydroxypentyf [f there is a carbonyl group in the branch (or a terminal COOH or its equivalent), its position (assigned lowest number when stereochemistry is being considered) is used to dcfme the confIgUrational prefix (see examples 1 and 3 in Chart V). Use of the R,S system is generally preferred, as less open to misinterpretation. For an alternative approach to naming carbohydrate residues as substibJents see 2-Carb-31.2 [which would give the name (lR)- or (IS)-L-arabinitol-I-C-yl for the ahove example, depending on the ligands at the branch point]. 2-Carb-18.5. Numbering The carbon atoms of the parent chain are numbered according to 2-Carb-2.2.1. If a unique numbering is required for the branch(es) (e.g. for X-ray or NMR work), the carbon atoms may be given the locant of the appropriate branch point, with the internal branch locant as superscript, e.g. 42 for position 2 of the branch at position 4 of the main chain. This style of branch numbering is not to be used for naming purposes: e.g. the side-chain-methylated derivative of compound 5 is named 4,6-dideoxy-3-C-[(R)-I-methoxyethyIJ-D-ribo­ hexose, and not as a 31-O-methyl derivative. 2-Carb-18.6. Terminal substitution See 2-Carb-16.4. 2-Carb-19, AldiMs 2-Carb-19.1. Naming Alditols are named by changing the suffIx '-QSC' in the name of the corresponding aldose into '-itol'. If the same a1ditol can be derived from either of two different a1doses, or from an aldose or a ketose, preference is ruled by 2-Carb-2.1 or 2.2.2 as appropriate. Examples:

?¥,H «H.<>H HO?"' HCOH HCOH I I HOCH HCOH I I HOCH HOCH I I HCOH HCOH I I HCOH HCOH I I cf¥)H C~OH D-glycero-o-galacto+feptito/ o-etytflro.t. -ga/acfo-Octitol noIl-gIycero-D-matIIIO-heplitol not o-tIwo-!.-gufo«titol 2797

9fl,oH HCOH «H,OH I HOCfl HOCH I I HCOH HCOH I I HCOfl HCOH I I CH,OH CH,OH

o-Arabinitol (Ara-ol) not o-IyxitoI o·GlucitoI (GkxII) not L-guUtoI (the lrivial name SOIbitoi is not recommended) The trivial names fucitol and rhamnitol are allowed for the a1ditols conesponding to the 6-deoxy sugars fucose and rhamnosc.

«liP« ~H HOCH HCOH I I HCOH HCOH I HboH HOCH I I HOCH HOCH I I CH3 ell:.

l-Fucitol (l-Fuc-olj or 1-deoxy-o-galactitol L·Rhamnitol (L-Rha-olj or l-deoxy-t..-mannitol not 6-deoXY-l-galactitoi (ct. 2·Carb-2.2.3.1)

2-Carb-19...2. meso Form.~ Alditols that are symmetric and therefore optically inactive - the meso fonns - can be designated by the prefix meso-. Examples: meso-Erythritol meso-flibitol meso-Galactitol The prefix D or L must be given when a derivative of a meso form has become asynunetric by substitution. It is also necessary to define the configurational prefixes as D or L in the case where there are more than four contiguous asymmetric carbon atoms. Eicamples:

~ HCOH CH:zOH I I HCOH HOYH I HCOH HOCH I I HOCH flOCH I H60H HCOMe I I CH,oH CHpl

meso-o-g/ycero-L·ido-Heptitol 5-OMeth~oI not l-g/ycero-O·ido-heptltot; ct. 2·Carb-2.2.3 oot 2-0-methyf·L-galaclitoi 2-Carb-20. Aldonic acids 2-Carb-20.1. Naming Aldonic acids are divided into a1dotrionic acid. aldotetronic acids, a1dopentonic acids. a1dohexonic acids, etc., according to the number of carbon atoms in the chain. The names of individual compounds of this type are formed by replacing the ending '-osc' or the systematic or trivial name of the a1dosc by ·-onic acid'. 2798

Examples:

COOH coo· COOH I I I HCOH HCOH I I ?Hz HOCH HOCH HOCH I I I HCOH HCOH HCOH I I I HCOH HCOH HCOH I I I C~H CH,.oH CH,.oH o-Gluconic acid o-Gluconate 2-Amino-2-deoxy-o-g/uconic acid 2-Carb-20.2. Derivatives Salts are named by changing the ending '-onic acid' to '-onate', denoting the anion. If the counter ion is known, it is given before the aldonate name. Example: Sodium D-gluconate Esters derived from the acid function are also named using the ending' -onate'. The name of the alkyl (aryl, etc_) group is given before the aldonate name. Alternative periphrase names like 'aldonic acid alkyl (aryl, etc.) ' may be suitable for an index. Amides are designated by the ending '-onamide', and nitriles by the ending '-ononilrile'. Examples:

/Me COOMe COOCH I I , HCOH HCOH Me I I ~ONMe2 HOCH HC-OM. HOCH I I I HCOH MeO-CH HCOH I I I HCOH HOCH HOCH I I I Ct¥>H CH"oH ~H

Methyl o-g/uconate Isopropyl3,4-di-O-methyl-l-mannonate N,N-Dimelhyl-l-xylonamide

COOMe COOMe I I HOCH HCOAc I I AcOCH ~ I AcOCH H?OH I CHzQH C~Ac Methyl 3-deoxy-o-threo-pentonate Methyl letra-().acety/-l-arab/nonate Lactones are named with the ending'-onolactone'. The locants must be given (in the form '-ono-ij-Iactone): that oftbe carbonyl group (I) is cited first, and that of the oxygen (;) second (see examples below). Periphrase names (see alternatives in parentheses) appear widely in the literature but are not reoonunended. Lactams are named similarly by use of the ending '-onolactam'. Examples:

C=O yt¥>H I Ctl2OH HCOH O I HOC~H0 yH2 OH H 0 HO~O\ • HO~ HO~O HCOH H OH 0 I HCO H OH I CH"oH

o-GIucono-1,4-/actone o-Gfucono-1,5-1actone 3-Deoxy-o-ribo-hexono-1,5-1actone (o-Gluconic acid'tlactone) (o-Gluconic acid ~ctone) 2799

HO~CH~NHOH HO o 5-Amino-5-deoxy-o-mannono-l.5-lactam Acyl halides are named by changing the ending '-onic acid' to '-onoyl halide'. Example:

COCI I HCOAc I AcOCH I HCOAc I HCOAc I Ct¥)Ac

Penla-O-acetyl-D-gluconoyf chloride More complicated examples of general principles for naming acid derivatives can be found elsewhere [13,14]. 2·Carb·21. Ketoaldonic acids 2-Carb-21.l. Naming Names of individual ketoaldonic acids are fonned by replacing the ending' -ulose' of the corresponding ketose by '-ulosonic acid', preceded by the locant of the ketonic carbonyl group. The anion takes the ending '-ulosonate'. The numbering starts at the carboxy group. In glycosides deri ved from ketoaldonic acids, the ending is '-ulosidonic acid' , with appropriate ring-size infix, e.g. '-ulopyranosidonic acid'. Examples:

COOH I CooH HOCH I I C=O HCOH I I HCOH HCOH I I HCOH c=o I I Ct¥)H CH:!OH

o-erythro-Pent-2-ulosonic acid o-Bmbino-Hex-5-ulosonic acid

yH,oH

H 0 COOH HOOC-CO~HHOCH I HKD~HC~ ~H HO '" HtfOH OK H HO OH HCOH H OH I CH. HO H H H

a-D-atabino-Hex·2-ulopyranosonic acid 3-Deoxy-«-o-manno-oct-2-ulopyranosonic acid Note. TIle last of the above examples is one of the possible forms of the compound referred to by the three-letter symbol Kdo (formerly the abbreviation KDO. from the previously allowed trivial name ketodeoxyoctonic acid). SimilMly the symbol Kdn for the C9 sugar 3-deoxy-o-g/ycero-o-galac/o-non-2-ulopyranosonic acid is widely used. 2-Carb-21,2. Derivatives Esters, lactones, lactams, acyl halides etc. are named by modifying the ending '-ic acid' as described for aldonic acids (2-Carb-20.2). 2800

Examples:

H ° COOEt QH HO HO OMe

HO H

Ethyl (methyl tx-o-arabino-hex-2-ulopyranosid)onale

Note. The parentheses are inserted 10 distinguish between the ester alkyl group (cited first) and (he glycosidic O-alkyl group.

H~OHO OH : HO o-c CH,OH (Jcj7" ~ H~ OH ~ I I °OH H OH H N o c=o H

jJ-o-Bmbino-Hex-2-ulopyranosono-1.5-lactone IndoI-3-yI o-xyla-hex-5-ulofuranosonate; lrivial name isatan B

rH,OH 1H,OH 1H20H HCOH 0 HC~OH0 HVO~O H 0 ~O ~">=<'- .. H H 0 HO OH OH 0

l-~~Hex-2-ulosono-1.4-lactone l-th~ex-2-enono-1.4-lactone L-Iyx~Hex-2-ulosono-1.4-lactone (L-AscortJlc acid is the equHibrium mixture of all three isomers)

2-Carb-22. Uronic acids 2-Carb-22.I. Naming and numbering The names of the individual compounds of this type are fanned by replacing (a) the '-ose' of the systematic or trivial name of the aldose by '-uronic acid" (b) the '-oside' of the name of the by '-osiduronic acid' or (c) the '-osyl' of the name of the glycosyl group by '-osyluronic acid'. The carbon atom of the (potential) aldehydic carbonyl group (not that of the carboxy group as in normal systematic nomenclature [13,14]) is numbered 1 (see 2-Carb-2.1, note I). 2-Carb-22.2. Derivatives Derivatives of these acids formed by change in the carboxy group (salts, eslers,lactones, acyl halides, amides, nitriles, etc.) are named according to 2-Carb-20.2. The anion takes the ending' -uronate' . Esters are also named using the ending '-uronate'. Examples;

CHO I HCOH I COOH 0 HOCH, HO ~OH HCOH, HO HCOH , OH COOH

o-Glucuronlc acid tx-o-Mannopyranuronic acid 2801

H 00Me COOH HO~O\ ~H H HO~OPh HO H H OH Phenyl fl-o-glucopyranosiduronic add Methyt a-L·idopyranosiduronic acid not phenyl fl-o-glucuronoside or phenyl glucuronide ~~ Or Methyl2.3.4·tri-().acety1-o:·o-glucopyranosyluronate bromide

o OM. H~OOMe H HO ~H HO HOCH H HOCH H I OH H I OH H CN COONa Methyl a'L-glucofuranosidurononitrile Sodium (methyl a-L-glucofuranosidjuronate COOEt CHO I HCOH BzOC~IH0 H I OBzBzO O-CH H OH ~JHCO, ;OH H H ljHCOH HCOBz I COOEt '=0 Ethyl 2.3.5-tri-().benzoykx-o-mannofuranuronate o-Glucur0n0-6,3-lactooe

O=C

Hoc~l~oH :~I~Oo H H,OH o H H H OMe H OH H OH

O-Gfucofuranuron0-6.3-lactone Methyl a-D-glucofuranoslduron0-6,3-lactone

COOH ~ ~"~ ~"~ H OH H OH

4-Deoxy-l-threo-hex-4-enopyranuronic acid Methyl 4-deoXY-l-threo-hex-4-enopyranuronate

c; DOMe QOH H H H OH

Methyl 4-deoXY-O:-l-lhr~hex·4-enopyranosiduronic acid 2802

OPh ~0H OH Methyl (phenyl4-Oeoxy-p-l-tflreo-hex-4-enopyranosid)uronate

HO ~q HO~OMe OH Methyl p-o-galaclopyranosiduronamide 2-Carb-23. Aldaric acids 2-Carb-23.1. Naming Names of individual aldaric acids are fOimed by replacing the ending' -05e' of the systematic or trivial name of the parent aldose by '-aric acid'. Choice between possible names is based on 2·Carb-2.2.2. Examples: COOH COOH 1 I COOH COOH HCOH HCOH I 1 1 1 HCOH HCOH HOCH HOCH 1 1 1 1 HOCH HOCH HOCH .. HCOH 1 1 1 1 HOCH HCOH HCOH HCOH 1 1 1 I HOCH HCOH HOCH HOCH I I 1 I COOH COOH COOH COOH l-Altrarlc acid o·Glucaric acid L-g/JII;ero.o-galacto-Heptaric acid noIl-taJaric acid not l-gularic acid not L-g~l1)-o-gluco-heptaric acid 2-Carb-23.2. meso Forms To the names of aldaric acids that are symmetrical. which therefore have no D- or L- prefix, the prefix 'meso-' may be added for the sake of clarity. Examples: meso-erythraric acid. meso-ribaric acid, meso-xylaric acid. meso-allaric acid. meso-galactaric acid. The D or L prefix must however be used when a meso-aldaric acid has become asymmetric as a result of substitution.

EXllITllIeS: COOH COOH I I COOH HCOH HCOH I 1 1 HCOH HOCH HOCH 1 1 1 HOCH HOCH Me(j-CH I I 1 HCOH HCOH HCOH 1 1 1 COOH COOH COOH meso-Xylaric acid meso-Galactaric acid 4-OMe1hyt-o-galactaric acid not 3·o.methyt-t-galactaric acid 2-Carb-23.3. Trivial names For the tetraric acids. the trivial name tartaric acid remains in use, with the stereochemistry given using the R.S system. Esters are referred to as 'tartrates' (the second 'a' is elided). Examples: COOH COOH I I «OOH HCOH HOCH HCOH 1 1 1 HOCH HCOH HCOH I 1 I COOH COOH COOH (2R.3R)- or (+)-Tartaric acid (2S.3$)- or (-)-Tartaric acid (2R,3$)' or meso-Tartaric acid orL-threaric acid or o-threaric acid or erylhraric acid 2803

Note. In the older literature. there is confusion about the use of D and L in the case of tartaric acids. It is therefore ~mmended to use the R.S system in this case. 2-Carb-23.4. Derivatives Derivatives fonned by modifying the carboxy group (salts, esters, lactones, lactams, acyl halides, amides. nitriles etc.) are named by the methods of 2-Carb-20.2. Dilactones, half-esters. arnic acids etc. are narned by the methods of [13, 14]. In cases of ambiguity, locants should be specified. Examples:

COOMe COOH CONH;, I I I HCOH HCOH HCOH I I I HOCH HOCH HOCH I I I HOCH HOC" HCOH I I I HCOH HCOH HCOH I I I COOH COOMe COOH 1-Methyl hydrogen D-galaclarale 6-Methyf hydrogen o-galactarale D-Glucar-1-amic acid

COOMe I HCOH I HOCH I HCOH Ji~ I HCOH I CONH2 o Methyl o-glucar-6-arnate L-Mannaro-1.4:6,3-dilactone 2-Ctub-U. O-SubstiJutWn 2-Carb-24.1. Acyl (alkyl) names Substituents replacing the hydrogen atom of an alcoholic hydroxy group of a saccharide or saccharide derivative are denoted as O-substituents. The •0-' locant is not repeated for multiple replacements by the same atom or group. Number locants are used as necessary to specify the positions of substituents; they are not required for compounds fully substituted by identical groups. Alternative periphrase names for esters, ethers. etc. may be useful for indexing purposes. For cyclic acetals see 2-Carb-28. Examples: HC=O I HCOAc I AcOCH I HooAc I HCOAc I CH~Ac Penta-D-acetyl-aklehyr»o-glucose 2.4-Di-().acetyI-6-().lriIyt·o-glucopyranose or afdehyr»o-glucose penlaacetate

6-o-Melhanesultonyt-o--gaJactopyranose Tetra-Q.benzoykx-o-glucopyranosyt bromide or o-galactopyranose 6-melhanesulfonale ::~~\ I~ OH

4.6·Di·o-methyI-a·o-galactopyranose 2804

Note. Acyl substilUenlS on anomeric OH are designated (as above) by O-acyl prefixes. Howevec, anomeric O-alkyl derivatives are named as glycosides (see 2-Catb-33). 2-Carb-24.2. Phospborus oxoacid esters 24.2.1. Plwsphates Of special biochemical importance are the esters of monosaccharides with phosphoric acid. They are generally termed phosphates (e.g. glucose 6-phosphale). In biochemical use, the term 'phosphate' indicates the phosphate R:Sidue regardless of the state of ionization or the counter ions. The prefix terms used for phosphate esters in organic nomenclature ([14], p.65) are 'O-phosphono-' and 'Q-phosphonato-' for the groups (HO)2P(O)- and (O,2P(O)- R:Spectively, bonded to oxygen. The term 'phospho-' is used for (HO)2P(O)- or ionized forms in a biochemical context (see reconunendations for the nomenclature of phosphorus -containing compounds [24». If a sugar is esterified with two or more phosphate groups. the compound is termed bisphosphate, trisphosphate etc. (e.g. fructofuranose l,6-bisphosphate). The term diphosphate denotes an ester with diphosphoric acid, e.g. adenosine Sf -diphosphate. Note. In abbreYialioas, a capital P is used to indicate a tenninal-P03Hz group or a non-terminal -P028- group (or dehydronated forms).

Examples: ~CI:f2OP03H,z HO 0 H~O\ HO ott ~PO,2- o-Glucopyranoae 6-(dihydrogan phosphate) a-o-Glucopyranosyl phosphate or 6·0ph0sph0n0-D1I\ucopyranose (biochemical usage: glucose I-phosphate) (Glcl P)

QP032- I ctIzOP032- CH,z 0 HO~ ~CHPO:l2-.OH OH H o-Glucopyranoae 6-phosphate o-Fructofuranose l,6-bisphosphate (often shortened to glucose 6-phosphate) (often shortened to fructose 1,6-bisp/1osphate) or 6-O-phosphonato-o-glucopyranose or 1,6-di-~hosphonalo-D-fructofuranose or 6-phospho-O-gfucose (GIc6P) or 1.6-bisp/105pho-o-fructoluranose (in a biochemical context) o ~.. COOH I HOOH ~ HO~ .. HOOPOaHz

3-Q.PhosphonaI~ phosphate a-o-GlucopyIanuronic acid or 3-phospho-t>glyceroyl phosphate 1-(dihydrogen phosphate) or 1,3-bisphospho-O- (for biochemical usage) (biochenical usage: glucuronate 1-phosphate) (GIM1 p) t:IHz ~N:CJ

oo_~NNII I 5· -O-P-O-P-O-<,:H,z 0 b- 8 H H H HO OH

Adenosine S"-diphosphate (ADP) or S'4tphosphoadenosine 2805

G-

CHoOH 0 H HN~ ,- 0 0 O)...-NJ QOH H II II" , HO O-~-O-~-O-~~ H OH 0- 0- H H ,. H H HO OH Uridine 5'-(a:-D-glucopyranosyl diphosphate) (trivial name uridinediphosphoglucose) (UDP-GIc)

NIi-z ft fN OH O-P-O-CIi-z 0 IL .. A /-lOCH. _ 0-I~OH H H6 0 CooH H AcNH~ HO OH H HO

Cytidine 5'-(5-acetamido-3,5-dideoXY-D-glyce~~galacto-non-2-ulopyranosytonic acid monophosphate) (CMP-~eu5Ac) 24.2.2. Plwsphonatu The following examples illustrate the use of phosphonate terminology for esters of phosphonic acid, HP(O)(OH)2. Forfonnation of the alternative (substitutive) names, see 2-Carb-31.2. Examples: o II HO-~-OC~H'0 OM. H H H H H HO OH Methyl J!-D-ribofuranoside 5-(hydrogen phosphonate) or methyl 5-deoxy-p-o-riboluranosid·5-yt hydrogen phosphonate

OH COOMe HN~CH3 ft O)...N HOCH.~ , 0 O-P-OC~'0 AcNH HO I OH H H H H H N3 H

3'-AZid0-3'~eoxythymidine 5'-[(methyl5-acetamido-3,5-dideoXY-D-glyce~-D-galacto- non-2·ufopyranosytonate) phosphonatel Derivatives substituted on phosphorus are named by standard procedures [13, 14]; e.g. P-methyl derivatives are named as methylphosphonates. Compounds with a phosphonate group linked by a P-C bond to a carbohydrate residue may be named as glycos-lI-ylphosphonates (cf. 2-Carb-31.2) or as C-substituted carbohydrates (cr. amino sugars, 2-Carb-14). Example: HO~O\ HO~OH OP(OMel2

2-Deoxy·2-dimethoxyphosphoryl-D-glucopyranose (this usage ol'phosphoryl' is given in (13), Section D. Rute 5.68. and (141. p. 65) or dimethyl 2-deoxy-D-glucopyranos-2.ylphosphonate 2806

24.2.3. Phosphinates Esters of phosphinic acid. H2P(0)(OH). are named by the same methods as used for phosphonates. For examples with two P-C bonds see 2-Carb-31.3. 2-Carb-24.3. Sulfates The prefix tenns used for sulfuric esters are 'O-sulfo-' and 'O-sulfonato-', for the groups (HO)S(O)2- and (O-)S(O)2- respectively, bonded to oxygen. Sulfates may also be named by citing the word 'sulfate' . preceded by the appropriate locant. after the carbohydrate name. Example:

HO H,OI-IO

HO~ o 101-1 so,-

a-o-Galactopyranose 2-5UHate or 2-O-sulfonato-a-D-galactopyr8llOse The mixed sulfuric phosphoric anhydride (PAdoPS or PAPS) of3'-phospbo-5'-adenylic acid is named as an acyl sulfate:

~ o 0 N£N o"-s-o-p-o-a.."If 0 ~• I ~ o 0- H H '" oil~N H

o~P-o" OH I 0-

3'-Phospho-5'-adenylyl sulfate (PAPS) 2-Corb-25. N-SubstitutWn Substitution, e.g. acylation, at the NH2 group of an amino sugar can be dealt with in two different ways: (a) The whole substiruted amino group can be designated as a prefix, e.g. 2-acetamido- (or 2- butylamino-) 2-deoxy-I>-glucose. For the purpose of the configurational prefix, the group is considered to take the place of the former OH group. (h) If the amino sugar has a trivial name, the substitution is indicated by a prefix preceded by an italic capital N. Note. In carbohydrate nomenclature. substitution at a heleroatom is normally indicated by citing the locant of the atlllCbed carbon atom, followed by a hyphen. and then the italicized heteroatom element symbol, e.g. 2-O-methyl. S-N·acetyL Substituents on the same kind ofheteroatom are grouped (e.g. 2.3,4-tri-O·methyl). and substituents of the same kind an: cited in alphabetical order of heteroatoms (e.g. 5-N-acetyl-4,8.9-tri-O-acetyl). The alternative format with superscript numerical10cants (e.g. tr,04,08.0 9_tctra2atyl). used in some other areas of natural product chemistry, is unusual in carbohydrate ruunes. ExalJ1>les: CH,OAc I HCN(Me)Ac I AcOCH I HCOAc I HCOAc I CHtOAc

1,3.4.5.6·Penta·O-ace!yl·2-deoxy·2·{N-meIhyIacetamido)-o-glucitol 2807

HO~ ~OH ~A<:NH OH ~ 2-Acetamido-2-deoxy-o-galactopyranose 2-Deoxy-2-sulfoanino-o-glucopyranose or N-acetyl-O-gaJaClosamine or N-sulfo-o-glucosamlne

MGIycoIoyI-a-neUl'8l'llilic acid (a.-NeUSGc) 5-N-AcetyI-4,8.9-tri·().acetykx-neuraminic acid (0 is il11llied in the trivial name) (a-Neu4.5.8.9AC4) 2-Carb-26. llIIranwkcultzr anh,drides An inttamolecular ether (commonly called an intramolecular anhydride), fonnally arising by elimination of water from two hydroxy groups of a single molecule of a monosaccbaride (aldose or ketose) or monosaccha­ ride derivative, is named by attaching the (detachable) prefix 'anhydro-' preceded by a pair of locants identifying the two hydroxy groups involved. Note. Detacbable prefixes are cited iu alpbabetical order along with any substituent prefixes. Exampfes:

0 H kf=i2jH H HOC~OeN " H H NeOCH H MaO MaO I HO 0" H CHO

3.6-Anhydro-2.4,5-tri-O-me\hyI-o-gfuC0ge 2,5-Anhydro·o-aKononitrile

HOC~OHO C"-l] tf MeOCH~1..... 0 0Me o H "OH " H " " OH " 0Me 1,5-Anhydro-o.galaclilol Methyl 3.6-anhydro-2,5-di-O-methyl-jH>-glucofuranosida

5-Acetarnkf0.2,6-anhydro-3,5-dkleoxy-o-g/)am>-I>-gallJcto.non.2-enonic acid (Neu2en5Ac) The compounds usually known as monosaccharide anhydrides or glycose anhydrides (earlier 'glycosans'). formation of which involves the anomeric hydroxy group, are named by the same procedure. In these cases the order of preference of ring size designators is pyranose > furanose> septanose. However, three- or four-membered rings should nonnally be cited as 'anhydro' if there is a choice. Trivial names for anhydro monosaccharides, though established by usage, are not recommended because of possible confusion with polysaccharide names based on the use of the termination' -au'. 2808

Examples: CHpH ~o OH OH OHR OH OH l,6-Anhydro-jH>-glucopyranose 2,7 -Anhydro-f}-D-altro-hepl-2-ulopyranose not 1,5-anhydro-u-o-glucoseptanose (older trivial name: sedoheptulosan) (older trivial name: levoglucosan) ~~ o 3,4,6-Tri-O-acetyl-1,2-anhydro-a-o-glucopyranose 1,6:3,4-0ianhydro-~-o-talopyranose not 3,4,6-tri-O-acetyl-1 ,5-anhydro-p-o-glucooxirose ~;~ HO'={

OH 01 1,4-Anhydro-p-o-galactopyranose 1,6-Anhydr0-3,4-dideoXY-iH>-g/yQ!ro-hex-3-enopyranos-2-ulose° (trivial name: Ievoglucosenone) 2-Carb-27. Intermolecular anhydrides The cyclic product of condensation of two monosaccharide molecules with the elimination of two molecules of water (commonly called an intermolecular anhydride), is named by placing the word 'dianhydride' after the names of the two parent monosaccharides. When the two parent monosaccharides are different, the one preferred according to the order of preference given in 2-Carb-2.1 is cited first. The position of each anhydride link is indicated by a pair of locants showing the positions of the two hydroxy groups involved; the locants relating to one monosaccharide (in a mixed dian hydride, the second monosaccharide named) are primed. Both pairs of locants immediately precede the word 'dianhydride', Examples: H 0 ~ ~o:H H: H HOHHOrt;>C HOH o I' 0 OH H H a-o-Fructopyranose Il-o-tructopyranose 1,2':1 ',2-dianhydride

a-o-Fructopyranose a-D-6OibopyraOO68 1,2':1',2-dianhydride OH

HOOCx;tH °hOH

HO o+o)·.... ·.~ H H HO (a-o-Gaiactopyranuronic acid) I!-L·rhamnopyranose 1 ,2':1 ',2-dianhydride 2809

2-Carb-28. Cyclic acetals Cyclic acetals formed by the reaction of saccharides or saccharide derivatives with aldehydes or ketones are named in accordance with 2-Carb-24.1, bivalent substituent names (fonned by general organic nomenclature principles) being used as prefixes. In indicating more than one cyclic acetal grouping of the same kind, the appropriate pairs of locants are separated typographically when the exact placement of the acetal groups is known. .Examples;

H~

• ooCH~OOH H H H 0 H O-CMe2 2.4-O-MethyienexyfltOl t.2-0-Isopropylidene-a:-o-glucofuranose ~:::::.~ OCH I HOCH I HCOH I ~,·HO~ ~CM"2 H2CO OMe

1 ,2:5,6-Di-O-isopropylidene-t>-mannitol Methyl (R)-4,6-O-benzylidene-a-o-glucopyranoside

Methyl {S)-2.3:(R)-4,6-di-O-benzylidene-a-o-allopyranoside

3,4,6-T ri-().benzoyl-((S)-I,2·().chloro(methoxy)melhylene}-lH>-mannopyranose

3,4,6-Tri-O-acetyl-a-o-gIucopyranose (R)-t ,2-(methyl orthoacelale) or 3,4,6-lri-().acetyl-[(R)-1.2-().(I-methoxyethylidene}]-a-o-glucopyranose Note 1. The last two examples contain cyclic ortho ester structures. These compounds are conveniently named as cyclic acetals. Note Z. In the last four examples, new asymmetric centres have been introduced at the carbonyl carbon atom of the aldehyde or that has reacted with the saccharide. When Icnown. the stereochemistry at such a new centre is indicated by use of the appropriate R or S symbol «( 13], Section E) placed in parentheses. immediately before the locants of the relevant prefix. 2810

2-Carb-29. Hemwcetals, hemiketals and their thio analogues The compounds obtained by transforming the carbonyl group of the acyclic form of a saccharide, or saccharide derivative, into the grouping:

or

(R = alkyl Or aryl) are named as indicated in 2-Carb-30, by using the terms 'hemiacetal', 'monothiohemiacetal', or 'dithio­ hemiacetal'(or the corresponding 'hemiketal' terms for ketone derivatives), as appropriate. The two isomers of a monothiohemiacetal are differentiated by use of 0 and S prefixes. Examples:

OEt SEt I I HCOH HCSH I I HCOOz HCOBz I I 8zOCH BzOCH I I HCOBz HCOBz I I HCOBz HCOBz I I C~OBz CHzOBz

(1 S)-2,3,4,5,6-Penta-O-benzoyl-o-gtucose (1 S)-2,3,4,5,6-Penta-O-benzoyr-o-grucose ethyl hemiacetal ethyl dithiohemiacetal

OCt SEt I I HCSH HCOH I I HCOBz HCOBz I I BzOCH 8zOCH I I HCOBz HCOBz I I HCOBz HCOBz I I C~OBz CHzOBz (1 R)-2.3.4,5.6-Penta-O-benzoyl-o-gtucose (1s)-2,3,4,5,6-Penta-0-benz0yI-01J/ucose O-ethyl monothiohemiacetal s-ethyl monothiohemiaretal Note. In these compounds carbon atom number 1 has become chiral. When known, the stereochemistry at this new chiral centre is indicated using the R/; system ([131, Section E). 2·Carb·30. Acetals, keta/s and their thlo analogues The compounds obtained by transfonning the carbonyl group of a saccharide or saccharide derivative into the grouping: , OR' C' or / 'SRl (R =alkyl or aryl) are named by placing after the name of the saccharide or saccharide qerivative the lenn 'acetal', 'monothioacetal' or 'dithioacetal' (or the corresponding 'ketal' tenns for ketone derivatives) as appropriate, preceded by the names of the groups R 1 and R2. With monothioacetals. the mode of bonding of two different groups R1 and R2 is indicated by the use of the prefixes 0 and S. Examples: /S-CH2 , He CH2 'f(OE112 yHzOH I"s-c~/ HCOH y<0EI12 HCOH I I HOCH HOCH HOCH I I I HCOH HeOH HCOH I I I HCOH ·HCOH HCOH I I I CHzOH CHzOH c~ o-Glucose diethyl acetal o-Fructose diethyl ketal D-Glucose propane-1,3-diyl dithioacetal 2811

SEt OM. I I HCOMe HCSMe I I HCOH HCOAc I I HOCH AcOCH I I HCOH HCOAc I I HCOH HCOAc I I CHzOH ~Ac (1 S)-O-Glucose S-ethyl (1 R)-2,3,4,5,6-Penta-O-aeetyl.o-glucose O-methyl monothioacatal dimethyl monothioacetal

Note, In tbe last two examples, carbon atom 1 has become chiral. When known, the stereochemistry at this new chiral centre is indicated by the R,s system, as specified in 2-Carb-29. 2-Carb-31. Names for monosaccharide !esidues 2-Carb-31.1. Glycosyl residues The residue fonned by detaching the anomerie hydroxy group from a monosaccharide is named by replacing the terminal '-e' of the monosaccharide name by '-yl'. The general name is 'glycosyl' residue. Tenns of this type are widely used in naming glyeosides and oligosaccharides. For examples (including glycosyl residues from uronic acids), see 2-Carb-33.2. The tellIl 'glycosyl' is also used in radicofunctional names, e.g. for halides such as the glucopyranosyl bromide in 2-Carb-24.1 and the mannopyranosyl fluoride in 2-Carb-16.I, and esters such as the glucopyranosyl phosphate in 2-Carb-24.2.1 and the mannopyranosyl nittate in 2-Carb-16.2. 2-Carb-31.2 Monosaccharides as substituent groups In order to produce names for structures in which it may be desirable for a non-carbohydrate portion to be cited as parent, prefix tellI\S are required for carbohydrate residues linked through carbon or oxygen at any position on the main chain. These prefixes can be formed by replacing the final 'e' of the systematic or trivial name of a monosaccharide by '-n-C-y\', '-n-O-yl' or '-n-yl' (if there is no ambiguity). In each case the term '-yl' signifies loss of H from position n. At a secondary position (e.g. in 2-deoxy-o-glucos-2-yl, below) the free valency is regarded as equivalent to OH for assignment of configuration. Examples:

CHO YH..­ I c=o -yNH2 I HOCH HOCH HO~O I I OMe HCOH HCOH 0- I I OH HCOH HCOH I I CH.oH CH,oH l-Deoxy-o-fructOS-l-yI 2-Amino-2-deoxy-o-glucos-2-yl (Methyl p-o-ribopyranosid·2-O-yI)

COO COO I I -COH HC- I I HOCH HOCH I I HCOH HCOH I I HCOH HCOH I I CHpH ~OH

o-Glucos-2-G-yl 2-Deoxy-o-glucos-2-yI The same endings can be used to form substituent prefixes for alditol residues. 2812

Examples:

fH20H I HOCH CHOH I I -CH HCOH I I HCOH HOCH I I HCOH HOCH I I C~OH CH.OH

3-DeoXY-D-mannitoI-3-yt L-Arabinitol-l-C-yI (ct 2-Garb-18A) (RISto be specified at C-l) The ending '-yl' without locants signifies loss of OH from the anomeric position (see 2-Carb-31.1). Loss of H from the anomeric OH is indicated by the ending '-yloxy', without locant. For examples see 2-Carb-33. The situation in which the anomeric OH is retained but H is lost from the anomeric carbon atom is indicated by use of the ending '-yl' without locants in conjunction with the prefix 'I-hydroxy-' (not by the ending '-I-C-yl'). N.B. In this case, the anomeric prefix a or II refers to the free valency, not the OH group. Example:

Cf¥)H HO~OH

HO

l-HydroXY-O:-D-allopyranosyt Examples of the use of substituent prefixes for carbohydrate residues:

AdJ~CHPAc~ OAe

AcO ~ I,,:;

COGI

4-(1-Acetoxy-2,3,4,6-tetra-O-acetyl-a-o-allopyranosyl)benzoyt chloride N-(l-DeoXY-D-'ructopyranos-l-yt)-L-alanine ~C~)N-o-CH3 C HO OH 2

N.N-Bis-(l-deoxy-D-lructopyranos-l-ylj-p-toluidine

5-(5'-Deoxyadenosin-5' -yt)-L-methionine (AdoMet) S{(1-Adenin-9-yt)-1,5-dideoxy-II-D-ribofuranos-5-ylJ-L-methionine (Irivial name 5-adenosytmethionine (SAM)) 2813

C~H,~ SOH H,C~OH H H H H H H H H OH OH OH OH

Bis(5-deoXY-~D-riboluranos-5-yl) disuHide or bis(5-deoXY-~D-riboluranos-5-YQdisuHane

C~OHO HO~OH O'C~OOH

(~-D-Glucopyranos-2-O-yl)acetic acid (more commonly named 2-0-caJb0xyme1hyl-/H>-g1ucopyranose; see 2-Carb-2.1, note 2)

CH,OH - HOOC-CO-CH2-0~O\ .. -~

(Methyl Cl-o-glucopyranosid-4-O-yl)pyruvic acid {or methyl4-0-(oxaJomethyl)-«-o-glucopyranosideJ

3-(~D-Glucopyrano$y!oxy)indole (or indol-3-y! ~o-glucopyranoside); trivial name indican

HO

HOCH2~OHP-.--r-X~H 0 cH,OH HO OMe OMe

X=o Methy! 2-~methyt 2-

Methyl ~-o-talopyranose-2-C.4-C-diylpho$phinite or 2-C.4-C-{methoxyphosphanediyl)-~o-glucopyranose or (2R,4S)-2-C.4-C-{melhoxyphosphanediyl)-~-o-'hreo-heXOPyrano$e 2814

H~ P H MeO~ Methyl (ethyl 2,4-dideoxy-P-o-glucopyranoside-2,4-diy1)phoSphinile or ethyl 2,4-dideoxy-2,4-(methoxyphosphanediyt)-jI-o-glucopyranoside Residues fanned by detaching two (or three) hydrogen atoms from the same carbon atom may be named similarly_ Example: ;F~Me H~ H OH

(Methyt 6-deoxy-IH>-glucopyranosid-6-ytldene)triphenyH.5-phosphane or methyl 6-c1eoxy-e-~5_phosphanylidene-IH>-glucopyranoside Note. Names based on phosphane, rather than phosphine or phosphorane, are used in this document, as recommended in [14). 2-Carb-32. Ra4icals, cations and anions Naming procedures described in this section follow the rcconunendations given in [25]. 2-Carb-32.1. Radicals Names fOf·radicals are fonned in the same way as those for the corresponding substituent groups (see 2-Carb-3L2)_ Examples: yHoOMe c=o , CHzOBn MeOCH I Bno~O\ HeO- I BnO~ HCOMe BrIO H I CH:!QMe

1,3,5,6-Teba-O-methyl-o-fructos-4-O-yl Telra-~zyI-D-glucopyranosyi

BnO~O\ BnO~ BnO"QMe

2,3,4,6-Tetra-CHIenzyI-1-methoxy-o-glucopyranosyi Carbenes are narned analogously by use of the suffIX •-ylidenc' _ Example:

OOMe HOO .. H OH

Methyl 2-deoxy-!H>-8I)IIhro-pentopyranosid-2-ylidene 2815

2-Carb-32.2. Cations Cations produced by fannal loss of H- from a carbon atom are denoted by replacing tenninal 'e' with the suffix' -ylium', in conjunction with appropriate locants and a 'deoxy-' prefix jf necessary (cf. 2-Carb-31.2). Examples:

HO, ,CHO H, ,CHO CH"OH C' C' I I HOCH HOCH .HOCH"otI; H I I HCOH HCOH OH H I HO HO HCOH I CH"OH <~H ~OH H OH + CH"OH

D-stabirJo.Hexos-2-C-yfium 2-Deoxy-D-a~hexos-2-ylium D-Glucopyranosyfium ~-n AcO 1,0 c· I ~

3,4,6-Tri-O-acetyl-l ,2-o.elhyfiumdiyl-a-o-aIIopyIanose

Cations fonned by hydronation of an OH group or at the hemiacetal ring oxygen are denoted by the suffIX '-O-ium', with numerical locant. Examples: MeO~O\ ~OMe QMe+OH"

Methyl 3,4-di-O-methyt·ll-o-nbopyranosid-2-O-ium

H Meo~' OMe OM. OM. Methyl 2,3,4-tri-O-methyl-p-O-ribopyranosid-5-O-ium 2-Carb-32.3. Anions Anions produced by fonnal loss of H+ from an OH group are denoted by the suffix '-O-ate', with numerical locant. Example: Meo~O OM. 0- OMe

Methyl 3,4-di-O-methyt-ll-o-ribopyranosid-2-().ate Anions produced by fonnal loss ofW from a carbon atom are denoted by the suffIX '-ide', with appropriate locants and a 'deoxy-' prefix if necessary (cf. 2-Carb-3l.2). Examples: HO, ...COO H ... CHO C- 'c- I I HOCH HOCH I I HCOH HCOH I I MeO HCOH HCOH I I CH.OH <~~("H 0Me CH"OH D-atabino-Hexos-2-C-ide 2-Deoxy-o-arabino-hexos-2-ide l,5-Anhydro-2.3,4,6-tetra-().methyi-o-glucltol-l-ide 2816

2-Carb-32.4. Radical ions Radical ions can be named by adding the suffix 'y!' to ion names. Alternatively, the words 'radical cation' or 'radical anion' may be added after the name of the parent with the same molecular formula, especially when the location of the radical ion centre is not to be specified. Examples:

.. oo ~~)OH H HO

H OH o-Glucopyranosiumyt. or o-glucopyranose radical cation

:H2OHO H,OH

HOQ OH

0- H 2-Deoxy-o·srabino-hexos·2·id-2.yt, or 2-<1eoxy-o-SlBbino-hexopyranos·2·ytidene radical anion 2-Carb-33. Glycosides and glycosy/ compounds 2-Carb-33.1. DefInitions Glycosides were originally defined as mixed acetals (ketals) derived from cyclic forms of monosaccharides. Example: CH.OH O HOI:;;\_~_:=v\ 'v~b;;'1 OMe Methyl a-o-glucopyranoside However, the term 'glycoside' was later extended to cover not only compounds in which, as above, the anomeric hydroxy group is replaced by a group -OR, but also those in which the replacing group is -SR (thioglycosides), -SeR (selenoglycosides), -NR IR2 (N-glycosides), or even -CR lR~3 (C-glycosides). 'Thio­ glycoside' and 'selenoglycoside' are legitimate generic terms; however the use of 'N-glycoside', although widespread in biochemical literature, is improper and not recommended here ('glycosylamine' is a perfectly acceptable term). 'C-Glycoside' is even less acceptable (see Note to 2-Qub.33.7). A glossary of terms based on 'glycose' is given in the Appendix. Particularly in naturally occurring glycosides, the compound ROH from which the carbohydrate residue has been removed is often termed the aglycone, and the carbohydrate residue itself is sometimes referred to as the 'glycone'. Note. 1be spelling 'aglycon' is often encountered. 2-Carb-33.2. GJycosides Glycosides can be named in three different ways: (a) By replacing the terminal '-e' of the name of the corresponding cyclic form of the monosaccharide by '-ide' and preceding this, as a separate word (the intervening space is significant), the name of the group R (see examples below). Examples:

0Et CH,OH H~OH H H (?d: OH HCOH OMe OH H06H, OH OH HO

Methyl a·o-gulofuranoside Ethyl ~·o-fructopyranoside not methyl-a-o-gulofuranoside 2817

~r;;d:O HQHO

Methyl (6Rj-o-gluco-hexodieldo-6,2-pyranoside Note. This is the 'classical' way of naming glycosides. It is used mainly when the group R is relatively simple (e.g. methyl, ethyl, phenyl). (b) By using the tenn 'glycosyloxy-', in the appropriate fonn for the monosaccharide, as prefix, for the name of the compound. Note_ This prefIX includes the oxygen of the glycosidic bond. An example is given in 2-Carb-31.2; more are given below. (c) By using the term 'O-glycosyl-' as prefix to the name of the hydroxy compound. Note. This prefIX does not include the oxygen of the glycosidic group. This is the appropriate method for naming natural products if the trivial name includes the OH group. The system is also used to name oligosaccharides (see 2-Caro-37). Examples:

CH_3 _C OH ctSB .. ··H COOHO HO~v\ 0 •••• HO~ H OH

(20S)-20·Hydroxy-5~regnan-3a-yI p-o-gluc:opyranosiduronic acid or (20S)-3a-(p-o-glucopyranosyloxyuronic acid)-5~regnan-20-01; for biochemical usage, pregnanediol 3-glucuronide

Note. A common biochemical practice would give the name (20S)-3a-(~-D-gJucopyranuronosyJoxy}-5Il-pregnan-20- 01. This practice of naming glyeosyl residues from uronie acids as 'glyeuronosyl' is unsatisfactory because it implies the acceptance of the parent name •glycuronosc' . However the use of a two-word substituent prefix (glycosyloxyuronic acid), ending with a functional class name. remains inherenlly problematic, since il contravenes general organic nomenclature principles [13,14]. The latter practice has the advantage of retaining homomorphic relationships between glycoses and glycuronic acids.

<;:HzOH

C-CH3 H o-Q-'Il__ II CtizOH o CN OH H 0 HO~O_9_H HO H O OH Ph H OH

4-Aeetylphenyl P-o-glucopyranoside (S)-~o-Glucopyranosylmandelon~rile or 4'-(P-o-glucopyranosyloxy)aeetophenone; or (s)-(p-o-glucopyranosyloxy)(phenyl)acetonitrile; trivial name picein trivial name sambunigrin

~ CHzOHo ~~ I H 0 ~ H O-CH2'''C''''NH, H 0 0 ° H I H OH ~OH H COOH OOH H HO H HO H H OH H OH

7 -(P-o-Glucopyranosyloxy)-8-hydroxycoumarin; dl-p-o-Xylopyranosyl-L -serine [(Xyl-)Ser] trivial name daphnin 2818

Glycosides can be named as substituenl~ by the methods of 2-Qub-31. Example:

O OMe /~OH H o H H o H OH

(Methyl 5-deoxy-jJ-o-xylofuranosid-5-yI) 2-( 4-hydroxy-3-methoxyphenyt)-7 -melhoxy' 5-(2-(methyl fl-o-xytofuranosid-5-O-ytcarbonyl}yjnyl}-2.3-dihydrobenzofuran·3~rboxytate 2-Carb-33.3. ThiogIycosides Names for individual compounds can be fanned, like those for g1ycosides, in Ihree ways, as follows. (a) By using the lelm thioglycoside, preceded by the name of the group R. (b) With the prefix 'glycosylthio-', followed by the name of the compound RH; this prefix includes the sulfur atom. (c) With the prefix' S-glycosyl-' (nol including the S atom). followed by the name of the !hio compound. Sulfoxides and sulfones can also be named by functional elass nomenclature (13, (4). Examples:

H~OH H H

H OH OH S-o-COOH

Ethyl 1-thlo-p-o-g!ucopymnoside 4-( a-o-Ribofuranosytthio)benzoic acid or ok:arboxyphenyl 1-thio-a-o-ribofuranoside

~Iucopyranosyl (2}-O{potassium sulfonato)but-3-enehydroxlmothioate (trivial name sinigrin)

C~OAc AcO~

Ph ..... s"O

Phenyl letra-O-acetyl-a-o-glucopymnosyl sulfoxide or phenyl2.3.4.6-telra-O-acetyf-1·lhio-a-O-g!uoopymnoside S-oxide 2819

2-Carb-33.4. SeIeooglycosides Names are formed analogously to those for thioglycosides (2-Carb-33.3). Examples: H 0 ~ H Se-CHz"«C-COOH H J HO~O\ H H NHz HO~Se[~ HOO H OH OH OH

2·Carboxyethyl 1-seleno,p-O-xyIopyranoside Se1I-O-Aibopyranosyl-O-~fenocysteine or 3-(JI-o-xyIopyranosyiselenolPropanoic acid or (6}2-amino-2-<:arboxyethyl1-sefeno.lJ-O-rilopyranoside or 3-(lJ-O·ribopyranosytseleno}o-afanlne 2-Carb-335. Glycosyl baJides Compounds in which the anorneric hydroxy group is replaced by a halogen atom are named as glycosyl halides. Pseudohalides (azides, thiocyanales etc.) are named similarly. Examples: CI¥>Ac 0 A~~

Bt Tetra-O-acetykx-o-mannopyranosyt bromide

Methyl (2,3,4-tri-O-acetyl-a-oil'ucopyranosyl)uronate bromide not methyl 2,3,4-tri-O-acetyl-1-bromo-1-deoxy-a-o-glucopyranuronate

BnO~O') BnO~!r o

3,4,6-Tri-O-benzyl-a-o-alllblno-hexopyranosyl-2·ulose bromide

3,4,5-Tri-O-benzyl-o.-o-alllbino-hexos-2-u1o-2,6-pyranosyl bromide or 3,4,5-tri-O-benzyl·alde/JydcHx-o-atabino-hexos-2-ulopyranosy! bromide

COOMe

CI

Methyl (5-acetamid0-4,7.8,9-tetra.O-aeetyl-3,5-dideoXY-D·~ro-o.-D·ga'acto-non-2-ulopyranosyt)onaIe chloride 2820

2-Carb-33.6. N-Glycosyl compounds (glycosylamines) N-Glycosyl derivatives are conveniently named as glycosylamines. In the case of complex heterocyclic amines. such as nucleosides. the same approach is used. Examples: J-°"SHzOO H~H~ OH H

N-Phenyl-a-o-fructopyranosylamine l-jl·D·RibofuranosylUl1lCiI (lrivial name undine) not aniline a-o-!ructopyranoside

~~>"~-{~~OH H NH2 HO H

H NHAe Nl-(2-Acetamido-2-deoxy-~lucopyranosyl)-L-lysinamlde (Lys·NH-GIcNAc) [trivial name N1-(N-ac:etytglucosammyl)-l-lysinamidej

NH;, ~Nh N N MeSC~20 H H H H HO OH

9-(S-5-Methyl-S·thio-p-o-riboluranosyt)adenine

COOH i H~-~-H CH2OHo 9H, H H NH-C=O

~OH H HO H

H NHAc

~-(2-Acetamido-2~..p..o.gIucopyranosyt)-l-aspamgine [(GIcNAc-)AsnJ Of 2-acetamido-N' -L-~rtyl-2-deoxy-p..o-glucopyranosylamine (trivial name p-N-acetyIglucoaaminyl-L-aspal8gine)

CONH:! HO~ HONH

ko.---"\"-CONH2 HO~OH HO

Bis{a-D-glucopyranosylu ronamide)amine 2821

2-Carb-33.7. C-Glycosyl compounds Compounds arising fonnally from the elimination of water from the glycosidic hydroxy group and an H atom bound to a carbon atom (thus creating a C.c bond) are named using the appropriate 'glycosyl-' prefixes (or other methods as appropriate, avoiding 'C-glycoside' terminology). Note. The term C-glycoside, introduced for naming pseudouridine (a nucleoside from transfer RNA), is a misnomer. Ail other glycosides are 'hydrolysabIe; the C-C bond of 'C-g1ycosides' is usually not. 'The use and propagation of names based on 'C-g1ycoside' terminology is therefore strongly discouraged. Example: Nx., HZN"1==('N

tizOH -.;::: COOH HOC~ON,.,NH HO ~0 I H H HO .6- H H OH HO H

4-~D-Glucopyranosylbenzoic acid 8-(2-Deoxy-(H>-el]/thnrpentofuranosyt)adenine not 4-<:arboxyphenyt C-p-o-glucopyranoside not adenine 8-(2-deoxyriboside) o HN~NHo

HOCHz 0 . ~H H H H HO OH

5-P-D-Ribofuranosyluracil; trivial name pseudouridine

HO~O\ HO~CHpI OH

3,7-Anhydro-2-deoxy·D·glycenro-gulo-ocloooo~rile or'2,C-(p'o-glucopyranosyl)acetonitrile not cyanomethyI C-p-o-gluoopyranoside

ti20H HO r 0 -.;::: OH HO 0 I I HO~ ~..6- H OH OH 0

2-p.o..Glucopyranosyl-1.3.6.7-tetrahydroxyxanthen·lHlne; trivial name mangiferin

OH 0 OH

CHzOH

(1 05)-1 0-~o-Glucopyranosyl-1.8-dihydroxy-3-(hydroxymethyf)anthracen-9( 1OH)-one; trivial names aloin A, (105)-barbaloin 2822

OH

OH 0 6·~·o·Glucopyranosyt·4',5,7·trihydroxy-8-O:-l·rhamnopyranosytflavone; lrivial name vioIanthin 2-Carb-34. Replacement of ring orygen by other elements 2-Carb-34.I. Replacement by nitrogen or phosphorus Names should be based on those of the amino sugars (see 2-Cacb· 14) (or the analogous phosphanyl sugars) with the amino or phosphanyl group at the non-anomeric position. Ring-size designators (furano, pyrano etc.) are the same as for the oxygen analogues. Examples: CHPi H HO~ HO OH

5-Amino-5-deoXY-D1!tucopymnose; trivial name nojirimycin CH:!OH H HO~

l-Amino-l,5-anhydro·l-deoxy-o-mamitol or 1,5-dideoxy-l,5-imino-o-mannitol; trivial name deoxymannojirimycin Note the extension of the use of 'anhydro' in the above example to include the elimination of water between -NH2 and -OH (cf. 2-Carb-26).

EI H Cf+..OHI HO HO~ HO~ HO OH OH OH OH

5-Deoxy·5-ethytamlno·a·o-glucopyranose 5-Deoxy-5-phosphanyl-o-xytopyranose Note. Use of the tenns 'aza sugar', 'phospha sugar' etc. should be restricted to structures where carbon, not oxygen, is replaced by a heteroatorn. Thus the structure below is a true aza sugar. The term 'imino sugar' may be used as a class name for cyclic sugar derivatives in which the riag oxygen atom has been replaced by nitrogen.

CH:!OH 0 HO~~ H 0Me

Methyl 3-deoxy-3-aza-O:-O-rilxH1exopyranoside 2-Carb-34.2. Replacement by carbon The (non-detachable) prefix 'carba-' signifies replacement of a heteroatom by caroon in general natural product nomenclature [261, and may be applied to replacement of the hemiacetal ring oxygen in carbohydrates if there is a desire to stress homomorphic relationships. H the original heteroatom is unnumbered, the new carbon atom is assigned the iocant of the non-anomeric adjacent skeletal atom, with suffix 'a'. 2823

Note. The draft natural product rules (26J recommend that the new carbon atom takes the locant of the lower-numbered proximal atom. However. carbohydrate chemists regard the ring oxygen as formally originating from the non-anomeric (usually higher-numbered) position. Additional stereochemistry (if any) at !he new carbon centre is specified by use of the RlS system ([13]. Section E). Structures of !his type can also be named as cyclitois [8]. Examples:

CH~H sa HO~ HO~OH OH

5a.(;arba-jl-o-glucopyranose

tflJl.CHa 0;")

••• HOC~.. H H I' H H HO H

1-(2-Deoxy-4a-carba-p..D-~ or 4'a-carbalhymidine oo~, H~~l ~ "'t---r'6HtOH HO H

5a-Carba-~-D-f1\JclOfuranosyf 5a-cama-a-D-g!ucopyranoside

1-{{4aS)-2-Deoxy-4a-fluoro-4a-caJba-1\-O-8I)'thn>pentofuranosyl)thymine or (4'aS)-4'a-ltuoro-4'a-carbathymidine 2-Carb-3S. Carbohydrates containing additional rings Internal bridging of carbohydrate structures by bivalent substituent groups creates additional rings. which can be named either by use of a substituent prefix representing !he bridging group, or by fusion nomenclature. The following recommendations for !he use of !hese two approaches are nol !horoughly developed; !hey simply represent an attempt to rationalize and codify current literature practice in the use of systems not in general well suited to carbohydrate applications. Bridging substituent prefix nomenclature (2-Carb-35.1) is based on the system well established for simple cyclic acetals (2-Carb-28), and fusion nomenclature (2-Carb-35.2) on current literature usage and requirements for general natural product nomenclature [26}. 2824

2-Carb-35.1. Use of bivalent substituent pref"lxes Where the new bridge is attached to oxygen (or a replacement heteroatom, e.g. nitrogen in an amino sugar) already indicated in the name of the unbridged carbohydrate, the bivalent substituent prefix denotes substitution at two heteroatoms as outlined in 2-Carb-24.1 and 2-Carb-25 [method (bl). Heteroatoms not directly bonded to the carbohydrate chain are regarded as part of the bridge. Where the new bridge is attached through C-C bonds to the carbohydrate chain, the bridge prefIX. denotes a double C-substitution. Procedures are as outlined in 2-Carb-16. Examples: O... ·_··(\;:.~H MJ ___ '>-\_/~e2 o· 0

2,3:4,5-Di-O-isopropylidene-Jl-o-fructopyranose Note 1. The alternative fusion name (see 2-Carb--35.2) is 2,2,2',2'-tetramethyl-4,4',5,5'-tetrahydro-(2,3,4.5-tetradeoxy­ jJ-o-fructopynmoso)[2,3-d:4,>d1bis[I,3)dioxole; this is clearly less desirable on grounds of complexity. Note 2. The use of prefixes ending in '-ylidene' for gem-bivalent substituent groups is traditional in the carbohydrate field, although no longer recommended in general organic nomenclature (14). CH3~~Me o 0 HO OMe

Methyl [(S)-4,6-0-(1-methoxycarbonylethylideneIHI-o-mannopyranoside

Methyl 2,3-(butane-l ,4--diyl)-2,3-

CH:!OH 0 OMe

HOg H 0.- .t'l

Methyl 2,3-(buta-l,3-

l,6-Anhydro-2,3-d"ldeoxy-2,3-{9,10-dihydroanthracene-9,10-diyl)-Jl-o-fibo.hexopyranos-4-ufose 2825

20 ~ BnO 0'1 Boa~ :::-....

(15)-1 ,5-Anhydro·3.4.6-tri-O-benzyl-l-C,2-().(o-phenyIenemethylene)-o-mannitol Note. The isomeric chromene would be named as a 2-0.I-e-substituted system_ The prefix 'cyclo-' may be used for a single-bond bridge [14]. Examples:

Methyl 4-N-acetyl-2.3-di-().acetyt-4,(HIiamin0-4,6-Nqclo-4,6-dldeoxy-«-o-gaIactopyranoside

Methyl 2.3-di-().acetyt-4,6-qc1o-4.6-dideoxy-Ik>ilalactopyranoslde 2-Carb-3S.2. Ring fusion methods Fusion methods are employed as in general natural product nomenclature [26], except that the original CMbobydrate ring is cited first, in parentheses (with terminal' -e', if present, replaced by '-0'). For designating stereochemistry, bonds in the new ring are considered as equivalent to OR, unless OR (or its equivalent) is still present at the ring junction. Substituents on the carl>ohydrate portion are included within the parentheses enclosing thC fusion prefix. Substituents on the new ring (including 'hydro-' prefixes) precede the carl>ohy­ drate term(s). If there is a choice, the new ring is numbered in the direction used to define the fusion locants. Note.. General natural prodllCt fusion nomenclature [26] would require the carbohydrate pottion to be cited last (e.g. oxazologlucopyranose). whereas it is cited first here and in the literature. Examples: CH"OH o HO~

Ph

2-Phenyl-4.5-dihydro-(1.2-dideoxy-a-D1Ilucopyranoso)(2,1-dJ-l.3-0xazole Note 1. The alternative name using a substituent prefIX (see 2-Carb-35.1) is 2-amino-J-O.2-N-{benzylylidene)-2-de­ oxy-a-o-glucopyranose. Note 2. Uterature fusion names for this type of compound USC 'glucopyrano{2,l-dloxazoline' terminology. How,ver, names for pattially hydrogenated heterocycles ending in •oline' were abandoned by RIP AC in 1983 [27]. in favour of ·dihydro...... o!e·. Use of 'pynmoso' rather than 'pyrano' is recommended roavoid confusion with the normal fusion prefix from 'pyran' and ro simplify rules for naming derivatives (e.g. glycosides). CH"OA<; AcO~ 11.0 MeNH/

2-Methylamin0-4,5-dihydro-(3,4,6-tri-O-acetyl.l.2-dideoxy-a-D1Ilucopyranoso){2,1-4-1,3-0xazole Note. The alternative name using a substituent prefix (see 2·Carb-35.1) is 3,4,6-tri-O-acetyl-2-amin

HO_~CH'OHO HO HNf'NPh o 3-Phenyltetrahydro-(l.2-dideoJcy-o:-o-glucopymnoso)ll.2-djimidazol-2-one Note. The alternative name using a substituent prefIX (see 2-Carb-35.1) is 2-amino-l.2-N-carbonyl-I.2-dideox y-l-N­ phenyl-a-D-glucopyranosylamine

2-Methyl-5.6-dihydro-(4-O-acetyl-l.2.3.6-letradeoxy-3-methyf-o:-t-nbo-hexopyranoso)[3.2. l-de]-4H-l.3-oxazine Note 1. The alternative name using a substituent prefIX (see 2-Carb-3S.I) is 4-0-acetyl-3-amino-2,3.6-trideoxy-I-O,3- N-{cthan-l-yl-l-yJidcne)-3-C-methyl-a-L-ribo-hexopyranose Note 2. This example would not nonnally be regarded as a fused system for nomenclature pwposes. since it is not oltM­ or ortho- and peri-fused [13]. 2-Carb-353. Spiro systems Spiro systems can be named by normal procedures (13). For clarity. any anhydro or deoxy prefixes or replacement prefixes (e.g. thio) refening to tbe spiro junction should appear next to the caJbohy­ drate stem. 1be carbohydrate component is cited first. Configuration at the spiro junction is assigned by the R,Ssystem. Example: A£O-y--=.",CtipAI: 0 0, AcU~-1N

Ph {1 R)-2,3.4.6-Tetra'O-acetyl-3'-phenyl$piroll.5-anhydro-o-glucitof-l.5' -{1.4.2]oxalhiazole)

(3&1-5-O-EIenzoyl-l ',2'-dllydro-l,2-O-isopropyfidenespiro{3-deoxy-a-o-el}lthro-penlofuranose-3.3'­ naphtho(l,2-ell.3JoxazinJ-2'-01 The following spiro example is best narned by use of a gem-bivalent substituent prefIX:

HOCH.! , OH ~OH Methyl2.3-().o-glucopyranosylidene-o:-o-mannopyranoside 2827

Stereochemistry at C-l of the glucose residue could be indicated as R or S, e.g. [( lR)-2,3-0-o-glucopyrano­ sylidene] ..... 2-Carb-36. Disaccharides 2-Carb-36.1. Def'mition A disaccharide is a compound in which two monosaccharide units are joined by a glycosidic linkage. 2-Carb·JIj.2. Disaccharides without a free hemiacetal group Disaccharides which can be regarded as fonned by reaction of the two glycosidic (anomeric) hydroxy groups with one another are named, systematically, as glycosyl glycosides. The parent (cited as the 'glycoside' component) is chosen according to 2-Carb-2.1. Both anomeric descriptors must be included in the name. Examples:

C~H 0 HO~

H~O0 OH

C~OH OH

a-o-Glucopyranosyl a-D-glucopyranoside ~D-Fructofuranosyl a-o-glucopyranoside [a-D-GIcp-(1 +-+1 )-a-o-Glcp) [jH>-Fru#-(2+-+1)-a-O-Gk:pJ (trivial name a,a-) not a-o-glucopyranosyl P-D-fruclofuranoside (trivial names sucrose, saccharose) Note. Such disaccharides are also known as non-reducing disaccharides. If derivatives are named on the basis of the trivial name, the component cited first in the systematic name receives primed locants. Example: 1~~~ o CIC~20 OH H CH~H HO

4,6,6'-Trichloro-4,6,6'-trideoxygalactosucrose or 6-chloro-6-deoxy-~o-fruclofuranosyl 4.6-dlchlor0-4,6-dideoxy-a-o-galaclopyranoside ('galactosucrose' is a trivial name for the 4-epimer of sucrose) 2-Carb-36.3. Disaccharides with a free hemiacetal group A disaccharide in which one glycosy\ unit has replaced the hydrogen atom of an alcoholic hydroxy group of the other is named as a glycosylglycose. The locants of the glycosidic linkage and the anomeric descriptor{s) must be given in the full name. There are two established methods in use for citing locants: either in parentheses between the glycosyl and glycose terms, or in front of the glycosyl prefix. as in the names of glycosides. The former (preferred) method is derived from that used to designate residues in oligosaccharides (see 2-Carb-37 and -38). Note. The latter method is thaI used by Chemical Abstracts Service for disaccharides. The O-Iocants used for the former method in the previous recommendations [I] are omitted here. 2828

Examples:

HO HO~CH20HO H20Ho HO ~ HO o~CH:.OH0 OHO~O\ OH HO HO~OH OH OH OH

a-o-Glucopyranosyt-{1-+4)-lkJ-glucopyranose JH>-Galactopyranosyt-( 1-+4)-«-o-glucopyranose [a-o-GIcp-{1-+4)-{I-o-GicpJ [JI-o-Galp-( 144)-a-o-G1cpJ Of 4-0-0:-o-glucopyranosyl-/l-o-glucopyranose or 4-Q.p-o-galactopyranosyl-a-o-glucopyranose (trivial name ~, not p-c-maltose) (trivial name a-, not a-O-lactose)

HO ~O. CH,DH 0 HO~O~,-:::,,, HO nv____ ~OH

p-o-Galactopyranosyt-{l-+4)-N-acetyl-o-glucosamine (trivial name N-acetylactosamine; LacNAc) Note. Disaccharides with a free herniacetal group are also known as reducing disaccbarides. 2-Carb-36,4 Trivial names Many of the naturally occurring disaccharides have well established trivial names. Some of these are listed below, together with the systematic names in both versions (see above). p-o-Glucopyranosyl-(1-+4)-o-glucose

4-Q.~-o-Glucopyranosyl-o-glucose Gentiobiose I\-D-Glucopyranosyl-(146)-O-glucose

6-Q.~o-Glucopyranosyt-D-gluoose ISOfOaitose a-o-Glucopyranosyt-( 146)-o-glueose 6-O-a-o-Glucopyranosyl-o-glucose Melibiose a-o-Galactopyranosyl-(I46)-o-glucose 6-0-0:-o-Galactopyranosyl-O-glueose Primeverose p-o-Xylopyranosyt-(I46)-o-g1ucose

6-0. ~o-Xylopyranosyl-D-glucose Rutinose a-l. -Rhamnopyranosyl-(146)-o-gJueose 6-0-0:-t.-Rhamnopyranosyl-o-glueose 1be systematic names of trehalose, sucrose, maltose and lactose have been given already (with the fonnulae). If derivatives are named on the basis of the trivial name, the component cited first in the systematic name receives primed locants. Example:

1,2,2',3,3",4',6-Hepta-Q.acetyI-6" -O-tosyI-«-a!lIobiose or 2,3,4-tri-Q.acetyl-6-Q.tosyl-p-o-glucopyranosyl-{1-+4)-1 .2,3,6-tetra-Q.acetyl-a-o-glucopyranose If the reducing terminal is a uronic ester glycoside, the ester alkyl group is cited at the beginning of the name, and the aglyconic alkyl group is cited with the name of the glycosidic residue. 2829

Example:

Methyl (3-O-acetyl-6-deoxy-2.4-di-Q-methykx-l-galactopyranosyl}-(1--+4}-(aIyI 2.3-di-O-benzoyt­ (J-o-gIuoopyranOSid)ulOO8le 2-Carb-37. Higher oligosaccharides 2-Carb-37.1. Oligosaccharides without a Cree bemiacetal group Trisaccharides (for example) are named as glycosylglycosyl glycosides or glycosyl glycosylglycosides as appropriate. A choice between the two residues linked through their anomeric positions for citation as the 'glycoside' portion can be made on the basis of 2-Carb-2.1. Alternatively, a sequential (end-to-end) naming approach may be used, regardless of 2-Carb-2.1. The names are fonned by the preferred method of naming disaccharides (see 2-Carb-36.3): the locant of the anomeric carbon atom, an arrow, and the 10cant of the connecting oxygen of the next monosaccharide unit are set in parentheses between the names of the residues concerned. Examples:

:~ HO~0«H20 HO OH ~~ OH

jl-o-Fructoluranosyt (X-O-galactopyranosyt-(1-+6)-Cl-D-glucopyranoside' (glucose preferred to fructose lor citation as 'glycoside') or (X·D-galactopyranosyl-{ 1-+6)-Cl-D-glucopyranosyt (J-D-fructofuranoside (sequential method) [(X-o-GalJr(1~6)-«-o-GIcp-(1H2)jl-o-Frufl (trivial name rafflllOSe) 2830

HO~ - H~

~~oH HO H CHo HO H I

HOCH~O0 H HO H CHz HO H I

HCX!H:!~OH HO H CH"OH HO H

P-o-FlUCIofuranosyl-(2-+ 1)-jI-o-fructofuranosyl-(2-+ 1)-4'-o-fructofuranosyla-o-glucopyranoside [p.-o-Fru~2-+ 1 )"'D-Fru~2-+ 1)-jk)..f'ru#-(2H 1)-«-o-G1cp I (trivial name nystose) If derivatives are to be named on tile basis of tile trivial name, the component cited last in the systematic name receives !ocants with no primes, the preceding component singly-primed locants, etc. However, naming of and higher oligosaccharide derivatives systematically is preferred, to avoid ambiguity. 2-Carb-37.2. Oligosacc:barldes with a free hemiacetal group An oligosaccharide of this class is named as a glycosyl[glycosyl],.glycosc, i.e. the is the parent Anomeric descriptors and locants are given as described in 2-Carb-37 .1. The conventional depiction has the reducing sugar (glycosc residue) on the right and the non-reducing end (glycosyl group) on the left. Internal sugar units are called glycosyl residues (the tenD 'anhycbosugar unit' is misleading and its use is discouraged). As Ihe reducing end is often converted into the corresponding alditol. aldonic acid or glycoside derivative, the more general term 'downstream end' has been proposed for this end of the molecule.

~s: HO~ HO-0:--0,

~\HO~

II-lH3lueopyranosy1-(1~ucopyranosyt-(1-t4)-D-gluoopyranose (trivial name panose)

HO~CHzOH Ctipi 0 HO o~v, OH HO~ CH"OH 0 gIycosyIlIfOUP HO OH O~ gIycosyIl1I3idue HO g~.e resldo::.. H IHH3lucopyranosy1-(1-t4)-1k>-g1ucopyranosyl-(1-t4)-o-gIucopyranose (trivial name cellotriose) 2831

NaOOC HO CHzOH

HoH~~o~O HO o AdiN COONa O~O\ _ ~H0 ONe HO~O HO HO

Methyl (sodium a-l-idopyranosyluronate)-(I-+4)-(2-acetamido-2-deoxy-a·DiJluoopyranosyt).(1 .... 4). (sodium Jl-O-glucopyranosyluronate)-(I-+3H~o--galactopyranoside {N22{a·L·ldopA·(I-+4)-a-o-GlcpNAc-(1 .... 4)·JH>--GlcpA-(1-+3)-jk>-GalpOMe}} Higher oJigosaccharides are named systematically in the same way. However, it is often preferable to give their structures by use of the symbolic approach outlined in 2-Carb-38). Trivial names for linear oligosaccharides consisting only of I-M linked Il-O·glucopyranosyl residues are maItoUiose, maItotelnlOSe elc. Similar naD1CS, based on the component sugar, are convenient for referring to other hom()-()ligosaccharides (e.g. xylobiose, galactotetraose), but such names should be used sparingly. Locants for naming substituted derivatives may be obtained by assigning roman numerals to the residues in ascending order starting from the reducing end. Example:

6'V_G-Tritylmaltotetraose Arabic numerals have also been used in this context, but confusion may result when component sugar residues have structural modifications (e.g. chain branches) requiring superscript locant numbers. The present recommendation follows long-established usage in glycolipids [21]. 2-Carb-37.3. Branched oligosaccbarides Terms designating branches should be enclosed in square brackets. In a branched chain. the longest chain is regarded as the parent. If two chains are of equal length the one with lower locants at the branch point is preferred, although some oligosaccharides are traditionally depicted otherwise, such as the blood group A trisaccharide exemplified below. Examples:

CI¥>H 0 ""~

HO~ 0 HO \ OHO~

OH OH

a-O-Glucopyranosyt-(1-+4)-(a-O-glucopyranosyl-(1->6)]·o--glucopyranose [or 4.6-d1-G-(a-o-glucopyranosyf}-o-glucopyranose] (trMai name isopanose) 2832 k;~~ H:;:H6OH 0 O~OHO?~

HoC 0 OH OH HO (5-Acetamido-3,5-dideoxy-O-glycercxr.-o-gaIacto-non-2-ulopyranosylonic acid)-(2-+3)..j3-0-galaclopyranosyl-(1-->3)­ (a-l-fucopyranosyl-(l-+4»)-2-acetamido-2-deoxy-o-glucopyllllllise or 5-N-acetyl-a-neuraminyl-<2-+3)-~-o-galactopyranosyl-<1-+3Ha-lAucopyranosyl-{1-+4»)'2-acetamido-2-deoxy-O­ glucopyranose {a-Neup5Ac-(2-+3)-~O-Galp-(l-+3)-[a-L -Fucp-(1-+4»)-D

2-Acetamido-2-deoxy-«-o-galactopyranosyl-(1-+3)-(a-L-fucopyranosyl-(1-+2)]-o-galactopyranose {a-o-GaipNAc-(l-+3)-[a-L-Fucp-(1-+2)]-o-Galp} (blood group A trisaccharide) 2--Carb-37A_ Cyclic oIigosaccharldes 37 _4_ L St!misyslt!maUc I'UlI1It!S Cyclic oligosaccharides composed of a single type of oligosaccharide unit may be named semisystematically by ciling the prefix ·cyclo'. followed by tenns indicating the type oflinkage [e_g_ 'malto' for a-(l ~)-linked glucose units], the number of units (e_g_ 'hexa' for six) and the termination '-ose' _ The trivial names a--cyclodextrin (a-eD) for cyclomaltohexaose, Ji--cyclodextrin (fJ-CD) for cyclomaltoheptaose and y--cy­ clodextrin (y-CD) for cyclomaltooctaose are well established. Example:

CycIomaltohexaose {a-cyclodextrin, (X--CD) 2833

Structures with linkages other than (1-44) should be named systematically (see 2-Carb-37.4.2). Note. The cyclic oligosaccbarides arising from enzymic transglycosylation of have been Ieferred to as Schard­ inger •. lbese names (and those of the cyclohexaamylose type) are not IeCOmmeoded. but the abbreviation CD is tolernted. Derivatives with the same substitution pattern on each residue can be named semisystematically by assigning a single multiplicative prefIx (e.g. hexakis. heptakis etc.) to the substituent prefIxes as a group. Example:

0Ma Heptakis(6-deoxy-6-iodo-2.3-dj.().methyl)cycfomaltoheptaose Derivatives with different substitution patterns on the various residues can be named by the method of 2-Carb-37.2. assigning a roman numeral to each residue. Example: O~ HOJ¥: OH HOO~ lf HO OH

O~~OH HO 0 HOH2C~OH JfO o %OH \ O~~OH HO "C"'""~o o %OH °

S'-Amioo-S'-

~N

OH CycIoheptakis-(1-+4)-(S-deoxy;x-o-gluco-heptopyrancisylurononitrile)

OH Cycloheptakis-(1 ..... 4)-(7-amin

The I~ isomer of cyclomaltohexaose should be named cyc!ohexakis-{I-Ki)-a-D-glucosyl, rather than cycloisomaltohexaose. 2.Carb-37.S. Oligosaccharide analogues Structures in which the linking glycosidic oxygen is replaced by -CHz- may be named by use of the replacement prefix 'carba-' (if. 2-Carb-34.2) for emphasis of homomorphic relationships. The oxygen replaced is given the loeant of the carbon alom to which it is auached in the residue with the lower roman numeral (ciled as superscript) (ej 2-Carb-37.2), with suffix 'a'. Example: HO~ III H0cq,~ .. - ~ liOj CHzOH

.. O~

I OH 4 "a,4I1a-Dichloro-4"a-QIrba-a- If the glycosidic oxygen link is replaced by -O-NH-, nonnal amino sugar nomenclature can be employe

O __ NH~CH.0 HO HO OH 4-(2,6-Dideoxy-4-thio-a-o-arabino-hexopyranosyloxyaminoj-4,6-dideoxy-a-o-glucopyranose 2·Carb-38. Use of symbols for defining oligostu:cluuide structures· 2-Carb-38.1. GeoecaI coDSideratiom Oligosaccharide and polysaccharide structures occur not only in me fonn but often as parts of glycopeptides or glycoproteins [11] or of glycolipids [21]. It can be cumbersome to designate their structures by using the reconunendations of 2-Carb-37. The use of three-letter sYmbols for monosaccharide residues is therefore recommended. With appropriate locants and anomeric descriptors, long sequences can thus be adequately described in abbreviated form. Symbols for the common monosaccharide residues and derivatives are listed in Table 2. They are generally derived from the corresponding trivial names. Abbreviations for substituents (see 2-Carb-1.16.2), preceded by locants, follow the monosaccharide abbreviations directly. 2-Carb·38.2. Representations ot sugar chains For writing the structure of an oligo- or poly-saccharide chain, the g1ycose residue [the 'reducing group', i.e. the residue with the me hemiacetal group or modification thereof (e.g. a1ditol, aldonic acid, glycoside)] should be at the right-hand end.. Also, when there is a glycosyllinkage to a non-carbohydrate moiety (e.g. protein, peptide or ) the glycosyl residue involved should appear at the right. Numbering of monosaccharide units, if desired, should proceed from right to left. 2-Carb-38.3. The extended form This is the fonn employed by the caJbobydcate databank CarbBank, and is preferred for most purposes. Each symb<>l for a monosaccharide unit is preceded by the anomeric descriptor and the configuration symbol. TIle

The recommendations presented here are a modified version of !he published 1980 recommendations [6]. 2835

Table 2. Symbols for monosaccharide residues and derivatives in oligosaccharide chains

Abequoae Abe lduronic acid IdoA Allose All Lyxose Lyx All Mannose Men Aplose ApI Muramic acid Mur ArabInose Ara Neuraminic acid Neu ArabInIIoI Ara~ N-AQelyIneuraminic acid Neu5Ac 2-Deoxyribose dRib N-AcelyI-24eoxyneur-2-enaminic acid Neu2en5Ac Fruclose Fru NGIyooIoyIneuI1lri1ic acid Neu5Gc Fucose Fuc: 3-Deoxy-o-mam0-0ct-2-u1osonlc acid Kdo Fucito! Fuc-ol Rharnno8e Aha GaIactoee Gal 3,4-Di-O-meIhyIIflase RhaS.4MII2 Galac:tosamine aa.. Psi N-AcetyIgaIadosamine GalNAc Quinowse Qui p-o-GaIacIopyranoee 4-suHata p..o.Galp4S Ribose Alb Glucose Gle RI:JoIIe 5-phosphaIe Aib5P Glucosamina GleN Ribulose RibuIo (or Rill) 2.3-Diamino-2.3-dIdeoxy-o-gluc:ose GIcN3N Sorbose Sor Glucitol Glc-oI Tagatose Tag N-Acetylglucosarnkle GIcNAc Talose Tal Glucuronic acid GIeA Xyl Ethyl glucop)'IaIluronata GlepA6Et Xylulose Xylulo (or Xu!) Gul 2-0MeIhyIxyI0se XyI2CMe Ido ring size is indicated by an italic/for furanose or p for pyranose, etc_ The locants of the linkage are given in parentheses between the symbols; adoubIc-beadcd arrow indicatesaliDkage between twoanomcric positions. In CarbBank, omission of alP. DIl., orjlp means that this structural detail is not known. Examples:

~1-+6) ...-o-GIcP-(1H2)-p..o-FNffor (see 2-carb-37.1) p..o-Glep-(1-t4)-p..o-Glep-(1-t4)-o-G/c forcellolriose (see 2-Carb-37.2) Branches arc written on a second line, or in brackets on the same line. Example: a-o-Glep 1 J. 6 a-o-GlcM1-t4)-o-G/c or a-o-GIcp-(1-t4)(a-o-GIcp-(1-+6»)-o-GIc not a-o-Glcp 1 J. 4 a-o-GIcp-(1-+6)-o-G/c (see (llJ. 2-Ca1b-37.3) 2836

The hyphens may be omitted. except that separating the configurational symbol and the th~-letter symbol for the monosaccharide.

Z-Carb-38.4. 11te condensed form In the condensed fonn, the configurational symbol and the letter denoting ring size are omitted. It is understood thal the configuration is D (with the exception of fucose and iduronic acid which are usually L) and that the rings are in pyranose fonn unless otherwise specified. The anomeric descriptor is written in the parentheses with the locants. Example: Gal(ex1-6)GIc(ex1-2IIIFruffor raffl/lOS8 For most purposes. the short fonn (2-Carb-38.S) is preferred when abbreviation of the extended fonn is desirable.

2-Carb-38.S. The short form For longer scqucnccs. it is desirable to shorten the notation even furthec by omitting (i) locants of anomeric carbon atoms. (il) the parentheses around the locants of the linkage and (iii) hyphens (if desired). Branches can be indicated on the same line by using appropriate enclosing marks (parentheses. square brackets etc.). Whenever necessary. configuration symbols and ring size designators etc. may be included. to maIce the notation more specific. ElCIII11PJe: GaICl-6Gfoa-PFrufor Gala.6GloaIJFruffor raffinose The following examples show all three representations of the same structure: Ca) extended foan 1H>-GaIp"c1-H)-JJ-o-G1cpNAc-(1-+2)-cx-o-Manp-(1-+ 3 f 1 ex-L-Fucp

(b) condensed form in two lines Gal(lJ1-4)G1cNAc(IJ1-2)Man{ex1- I Fuc(Cl1-3)

or in one line GaI(lJ1-4)[Fuc(ex1-3)JGIcNAc(P1-2)Man(a1-

(e) short form GalIJ-4(Fuca-3)GlcNAcji-2Mana­ or Ga!p4(Fuca3)GIcNAcjI2ManCl­ or GalIWGIc:NAc:II2Manc- I Fuca3

This lISt version is recommended as the most explicit representation of branching using the short fann. Note. These rep_18lioDs do not follow !he recommcndalions for dJoic:e of main chain given in 2-CaJb.37.3. Such deviations are common in depicting series of naturally oa:arring oligosaccharides where it is desirable to show homomorphic relationships. 2837

2-Carb-39. Polysaccharides· 2-Carb-39.1. Names for homopolysaccharides A general tenn for a polysaccharide (glycan) composed of a single type of monosaccharide residue is obtained by replacing the ending' -ose' of the sugar name by '-an'. Note. ElIarnples of established usage of the '-an' ending are: xylan for polymers of xylose, mannan for polymers of mannose. and for polymers ofgalactose. Cellulose and starch are both $, as they are composed of glucose residues. 2-Carb-39.2. Designation of configuration of residues When the configurational series of the monomer residues is known. D- or L- may be included as a prefix to the name. Examples:

!4)-a-o-GIcP-{1-t3)-a-o-Glcp-{ 1-+In

A O-glucan (nigeranl

[5}«-l-Araf-(1 .... s)-a-L-Amf.(1-45)-a-l-Aral-(1 .... 5}«-t-Araf.(1 .... )n 3 3 t t

«-l-Amf a·L-Ara'

An l·arabinan (more specifically an a-l·arabinan) 2-Carb-39.3. Designation of linkage When the major linkage in a homopolysaccharide is known, it may be indicated in the name. The linkage designation shows the carbon atoms involved in the glycosidic bonds. When specific sugars are designated. notation for glycosidic linkages should precede the symbols designating the configuration of the sugar; thus. (l-+4)-a-D-glucan. Examples: ~9J }-1 H l n

(2-41)-II-D·Fructofuranan ( has this structure. with a tenninal «-D-glucopyranosyi group)

(4)-a-o-Gtcp.(1-t)n

(l->4)-a-D-Glucopyranan () Note. When the linkage between monosaccharide units is non-glycosidic (as in the phosphate derivative shown below). use of the glycan terminology is inappropriate; other methods of polymer nomenclature sbould be employed (20).

This is a modif'red version of the 1980 recommendations on polysaccharide nomenclature (7). 2838

HHH ft1 "i ~-",,-&:;g;;&.-~1- "" HO OH n PoIY[(l!-D-ribofuranosyl-5-().yI)(l-<1eoxy-o-ribi1o1-1-C,5-O-diy!)(oxidophosphotyl)] [5)-JH>-Albf-(1 .... 1)-D-Rib-ol-5-P-(O .... ]n Such structures do notconfonn to the original strict definition of 'polysaccharide' but are generally classified as polysaccharides in current practice. 2-Carb-39.4. Naming of newly discovered polysacdmrides Names assigned to newly discovered polysaccharides should end in '-an', ElClImples:

Pustulan (8 gIucan from the lichen Umbi/icaria pustufata)

c;tf:,OH OH C!¥)H HO~q HO-r--0---0~q ~~ OH H O~0-t..r-J HO~O f OH ~ OHHOO HO n

(3)-ll-o-GIcP--{1-+4)-ll-o-Glcp\-( 1.... 4)-l!-D-G1cp--{ 1.... 4)-«-l-Rhap-(1 ....ln

Gellan (8 bacterial potysaccharide originally designated S-60) Note. The name ending in '-an' refers to the unsubstituled polysaccharide. Thus xyJan occurs in nature in unacetylated and partially acetylated fonns. Xylan designates the unacetylated material, and xylan acetate an acetylated derivative. Well established names such as cellulose, starch, inulin, , amylose and are retained. 'Camlgeenan' and 'laminaran' are now often used rather than the older names ending in '-in'. 2-Carb-39.5. Uronic acid derivatives. A polysaccharide (glycan) composed entirely of glycuronic acid residues is named by replacing'-ic acid' by '-an'. The generic name for this group of polysaccharides is 'glycuronan'. Example:

(1-+4)-cx-o-galac:turonan ( component) Note. The tenn glycuronan is used instead of 'polyuronide'; the latter tenn is iIIc.omct. 2-Carb-39.6. Amino sugar derivatives A polysaccharide composed entirely of amino sugar residues is named by appropriate modiftcation of the systematic amino sugar name. 2839

Example:

(4)-fH>-Glcp NAc(l-+)n

(1->4)-2-acetamido-2-deoxy-lk>-glucan (chitin) 2-Carb-39.7_ Polysaecbarides composed of more than one kind of residue A heteropolysaccharide (heteroglycan) is a polymer containing two or more kinds of sugar (glycose) or modified sugar (e.g. aminodeoxyglycose or glycuronic acid) residue. When the polysaccharide has a principal chain ('backbone') composed of only one type of sugar residue, this residue should be cited last (as a 'glycan' term), and the other types of residue cited as 'glyco-' prefixes in alphabetical order. Howevec, when no single type of sugar residue constitutes the principal chain, all sugar residues should be cited alphabetically as 'glyco-' prefixes, and the name should terminate with the suffIX' -glycan'. Examples: a-lrGalp. 1 J. 6 [4)-jl-o-Manp{1-.4)-fk>-MaIll>"{1-o1n

A o-gaJacto-o-mannan (guaran) Note. A less branched o-galacto-D-mannan could be shown in the short fonn as:

Gala~ GaJa~ I I {4Manp-ln4Manp-{4Manjl-]n4Manp-.

[4)-1H>-GIcp-(1-t4)·Il-o-GIcp-(1-+Jn 3 t 1 Il-D-MaIll>"{1-t4)-~GlcpA·(l-02)-a-o-Manp6Ac 6 4 \I CHaCC02-

Xanthan

2-Carb-39.8. Substituted residues When substitution occurs in a polysaccharide (glycan), each type of substitutent is cited in the name at an appropriate position (in alphabetical ordec). Examples:

O~O\ HO~O~O\ OH HO~O OH '-'L_~ __'A LO~~HOH HO~OMe OH (4-Q.Methyl-a-o-glucurono)-D-xylan 2840

OH

2,3-Oi-().acetyf-6-().lrityfamyfose

(4)'il-O-GlcpA-{1 ~3)1l-D-GfcpNAc-{1 ~In (2-Acetamldo-2~xy-o-gluco)-o-glucuronogtycan (hyaluronic acid orhyaluronan) 2·Carb·39_9. Glycoproteins, glycopeptides and peptidoglycans Polymers containing covalently bound monosaccharide and amino-acid residues are tenned glycoproteins, glycopeptidesor peptidoglyC3nS. It is not possible to give precise distinctions between these terms. [n general. glycoproteins are conjugated proteins containing either oligosaccharide groups or polysaccharide groups having a fairly low relative molecular mass. ProteogIYcans are proteins linked to polysaccharides of higb molecular mass. Peptidoglycans consist of polysaccharide chains covalently linked to peptide chains. The nomenclature of these compounds is discussed in (11 J. Synthetically produced or modified carbohydrate-protein conjugates are sometimes referred to as neoglyco­ proteins. The nomenclature for the carbohydrate-containing substituents in such structures is analogous to sequential oligosaccharide nomenclature (2-Carb-37.2) Examples:

O-ICH24NH (01 protein)

HO~ OMe CH.oMe 0 [ ~~~c-r---o--} OH 't-z;-{ OMe

Pofy-{(3.6-Di-().rnethyl-ll-o-glucopymnosyl)-(1-f4)-(2,3-di-().methyl-«-t.-Ihamnopyranosyl).(1~2)-(3-0-methyI-a-t.­ lhamnopynmosyloxy)-(1-0-+9)-nonanoyl-(1--tN)-protein {[Il--o-GlcpS.6Me2-(1-f4)-o:-t.-Ahap2.3Me:!-(1 ~2)-«-L-Rh~l..o-.9)-nonanoyt-(l ~N)".proteinl

00ICH,lr-Co-} NH (of protein) .:;c-r--o--} ~ C~e 0 [H~~C"7-0--} OH ~ 0Me

PoIy-{{3.6-Di.().methyl-ll-o-glucopyranosyl)-(1~4)-{2.3-di.0methyI-«-L-rhamno~ranosyf)-{1~)-(3-().methyI-«-L­ rhamnopytanosyloxy)-(1-0-+4')-(3-phenylpropanoyl)-(1~N ~ein 2841

References 1. IUPAC Commission on the Nomenclature of Organic Chemistry (CNOC) and IUPACIUB Commission on Biochemical Nomenclature (CBN), Tentative rules for carbohydrate nomenclature. Part I. 1969, Biochem J., US, 673-695 (1971); Biochemistry, 10,3983-4004 (1971); Biochim. Biophys. Acta, 244, 223-302 (1971); Eur. J. Biochem., 21.455-477 (1971) and 25, 4 (1972); J. Bioi. Chem., 247, 613-635 (1972);ref.2, pp.127-148. 2.lntemational Union of Biochemisuy and Molecular Biology, 'Biochemical Nomenclature and Related Documents', Portland Press, London (1992). 3. IUPAC-IUB Ioint Commission on Biochemical Nomenclature (JCBN), Conformational nomenclature for five- and six-memhered ring forms of monosaccharides and their derivatives (Recommendations 1980), Eur.J.Biochem. Ill, 295-298 (1980); Arch. Biochem. Biophys., 2fY1, 469-472 (1981); Pure Appl. Chem .• 53, 1901-1905 (1981); ref. 2. pp. 158-161. 4. IUPAC-IUB Joint Commission on Biochemical Nomenclature (JCBN). Nomenclature of branched-chain monosac­ charides (Recommendations 1980), Eur. J. Biochem .• 119. 5-8 (1981); corrections: Eur. J. Biochem., 125. 1 (1982); Pure Appl. Chent., 54, 211-215 (1982); ref.2, pp. 165-168. 5. IUPAC-IUB 10int Commission on Biochemical Nomenclature (JCBN). Nomenclature of unsaturated monosaccha­ rides (Recommendations 1980), Eur. J. Biochem •• 1l9. \-3 (1981); corrections: Eur. J. Biochem .• l25, 1 (1982); Pure Appl. Chem. 54.207-210 (1982); ref.2. pp. 162-164. 6. IUPAC-IUB 10int Commission on Biochemical Nomenclature (JCBN). Abbreviated terminology of oligosaccharide chains (Recommendations 1980),1. BioL Chern., 257, 3347-3351 (1982); Bur. J. Biochem.,126, 433-437 (1982); Pure Appl. Chem., 54, 1517-1522 (1982); Arch. Biochern. Biophys., 220,325-329 (1983); ref. 2, pp. 169-173. 7. IUPAC-IUB Ioint Commission on Biochemical Nomenclature (JCBN). Polysaccharide nomenclature (Recommen­ dations 1980), Eur. J. Biochem.,126, 439-441 (1982); Pure Appl. Chern., 54,1523-1526 (1982); J. Bioi. Chern., 'JS1, 3352-3354 (1982); Arch. Biochem. Biophys .• 220,330-332 (1983); ref. 2. pp. 174-176. 8. IUPAC-IUB Commission on Biochemical Nomenclature (CBN). Nomenclature of cyclitois (Recommendations 1973), Biochem. J .• 153, 23-31 (1976); Eur. J. Biochem., 57,1-7 (1975); Pure Appl. Chem., 37, 283-297 (1974); ref. 2, pp.149-155. 9. Nomenclature Committee of IUB (NC-IUB). Numbering of atoms in myo-inositol (Recommendations 1988), Biochem. J .• 258. 1-2 (1989); Eur. J. Biochem. 180.485-486 (1989); ref.2. pp. 156-157. 10. IUPAC-IUB Joint Commission on Biochemical Nomenclature (JCBN), Symbols for specifying the conformation of polysaccharide chains (Recommendations 1981). Eur. J. Biochem. 131. 5-7, (1983); Pure Appl. Chern., 55. 1269-1272 (1983); ref. 2, pp. 177-179. 11. IUPAC-IUB Joint Commission on Biochemical Nomenclature (JCBN), Nomenclature of glycoproteins, glycopep­ tides and peptidoglycans, EIlT. J. Biochem., 159, 1-6 (1986); J .• 3, 123-124 (1986); J. BioL Chem .• 262, 13-18 (1987); Pure Appl. Chem., 60, 1389-1394 (1988); Royal Society of Chemistry Specialist Periodical Report. 'Amino Acids and Peptides', vol, 21, p. 329 (J990); ref. 2, pp. 84-89. 12. IUPAC-IUB lointCommission on Biochemical Nomenclature (JCBN),Nomenclatureof g1ycolipids, in preparation. 13. ITJPAC Nomenclature of Organic Chemisuy. Sections A, B. C, D, E, F and H, 1979 Edition, Pergamon Press. Oxford, U.K. Sections E and F are reprinted in ref. 2, pp. 1-18 and 19-26, respectively. 14. Guide to IUPAC Nomenclature of Organic Compounds, Recommendations 1993. Blackwell Scientific Publications. Oxford (1993). 15. This text is largely based on an essay entitled 'Development of Carbohydrate Nomenclature' by D. Horton, included in 'The Terminology of Biotechnology: A Multidisciplinary Problem' (ed. KL. Loening. Springer-Verlag. Berlin and Heidelberg, 1990). 16. E. Fischer, Ber.• 23. 2114 (1890). 17. Rules of carbohydrate nomenclature (1948), Chern. Eng. News. 26, 1623 (1948). 18. Rules of carbohydrate nomenclature (1952), J. Chem. Soc., 5108 (1952); Cht!m. Eng. News. 31, 1776 (1956). 19. Rules of carbohydrate nomenclature (1%3), J. Org. Chem .. 28, 281 (1%3). 20_ IUPAC Commission on Macromolecular Nomenclature. Nomenclature of regular single-strand organic polymers (Recommendations 1975), Pure AppL Chem., 48. 373-385 (1976); 'Compendium of Macromolecular Nomenclature', Blaclcwell Scientific Publications, Oxford, p.91 (1991). 21. IUPAC-JUB Joint Commission on Biochemical Nomenclature (JCBN). The nomenclature of (Recommen­ dations 1976). Eur. J. Biochem., 79, 11-21 (1977); Hoppe-Seyler's Z Physiol. Chem., 358, 617-631 (1977); Lipids, 12, 2842

455-468 (1977); Mol. Cell. Biochem., 17, 157-171 (1977); Chem. Phys. Lipids. 21, 159-173 (1978); J. Lipid Res., 19, 114-40728 (\978); Biocht!m. J., 171, 21-35 (1978): ref. 2, pp. 180-191- 22. D. Cremer and lA. Pople. J. Am. Chem. Soc., ':Y1, 13S4-I3S8 (1975): J.C.A. Boeyens, J_ Crysr. Mol. Srrucr., 8, 317-320 (1978); P. KolI, H.-G.lohn, and J. Kopf, Liebigs Ann.. CMm., 626-638 (1982). 23. IUB Nomenclature Committee, 'Enzyme Nomenclatun:'. Academic Press, Orlando, Florida (1992). 24. IUPAC-fi1B Commission on Biochemical Nomenclatun: (CBN). Nomenclature of phospborus-containing com­ pounds of biochemical imponance (Recommendations 1976), HQPpe-~lers Z. PhysiQI. Chel1l., 358, 599-616 (1977); Ellr. J. Biodron., 79,1-9 (1917); Pmc. NatL Acad. Sci. USA. 74,2222-2230 (1977); Biochi!m. J., 171, 1-19 (1978); ref. 2. pp. 256-265. 25.IUPAC Commission on Nomenclature of Organic Chemistry. Revised nomenclature for radicals. ions, radical ions and related species (Recommendations (993), PUTe Appl. Chent.. 65, 1357-1455 (1993). 26_1UPAC Nomenclatun: of Organic Chemistry, Section F, revised version in preparation. 27. IUPAC Commission on Nomenclature of Organic OIcmistry. Revision of the extended Hanttsch-Widman system of nomenclature for heteromonocycIes, PUTe Appl. Chem., 55, 409-416 (1983). 2843

APPENDIX Trivial Names for Carbobydrates and Derivatives with their Systematic Equivalents and Symbols (non-limiting list)

(a) parent monosaccharides

Allose (All) aUo-Hexose Altrose (All) altro-Hexose Arabinose (Ara) arabino-Penlose

Erythrose etyth~ Tetrose

Erythrulose g/~Tetrulose Fructose (Fru) al8bino-Hex·2-ulose o-Fucitol (o-Fuc-ol) 6-0e0xy·o-gatactitol L -Fucitol (L-Fuc-ol) 1·0eoxy-o-galaclitol Fucosamine (FucN) 2·Amino·2,S-dideoxygalactose Fucose (Fue) 6-Deoxygalaclose Galactosamine (GaiN) 2·Amino·2o{leoxygalactose o-Galactosaminitol (GaIN-oI) 2-Amino·2o{leoxy-o-galactitol Galactose (GaO galacto-Hexose Glucosamine (GleN) 2·Amino-20{je0xyglucose Glucosaminitol (GlcN-ol) 2·Amino-2o{leoxyglucilol Glucose (GIc) gIuco-Hexose Glyceraldehyde 2.3-Dihydroxypropanat Glycerol (Gro) Propane·1.2.3-triol Glycerone 1 ,3-Dihydroxypropanone (1,3·) Gulose (Gul) guJo-Hexose Idose (Ido) ido-Hexose Lyxose (Lyx) /yxo-Penlose Mannosamine (ManN) 2-Amino·2.deoxymannose Mannose (Man) manno-Hexose Psicose (Ps9 ~ex-2-ulose Quinovose (Qui) S-Deoxyglucose Quinovosamine 2·Amino-2.6o{jideoxyglucose Rhamnitol (Rha-ol) l-Deoxymannilol Rhamnosamine (RhaN) 2-Amino-2.6o{jideoxymannose Rhamnose (Rha) S-Deoxymannose Ribose (Rib) ribo-Pentose

Ribulose (Rul) el)lth~Pent·2-ulose

Sorbose (Sor) ~Hex·2-ulose Tagatose (Tag) (y,Jro-Hex·2·ulose Talose (Tal) ta/o-Hexose Tartaric acid ErylhraricIThrearic acid rhnlD-Tetrose Xylose (XyI) xylo-Penlose Xylulose (Xul) /hn1D-Pent·2-ulose 2844

(b) common trivial names

Abequose (Abe) 3,6-Dideoxy-o-xy/o-hexose . Amicetose 2,3,6-Trideoxy-o-ef}'thra-hexose Amylose (1 .... 4)-a-o-Glucopyranan Apiose (Api) 3-C-(Hydroxymethyf)-glycero-tetrose Arcanose 2,6-Dideoxy-3-C-methyf-3-O-methyl-xy/o-hexose Ascarylose 3,6-DideoXY-l-atabino-hexose Ascorbic acid L-thlBO-Hex-2-enono-l,4-lactone Boivinose 2,6-Dideoxy-o-gulose Cellobiose p-o-Glucopyranosyf-(1-+4)-Oijlucose CeUotriose p.o-Glucopyranosyt-(I-+4)-/Hl-glucopyranosyt-(I-+4)-o-glucose Chacotriose cx-l-Rhanmopyranosyf-(I .... 2)-(a-L..mamnopyranosyf-(I .... 4Jl-o-glucose Chalcose 4,6-Dideoxy-3-O-methyl-o-xy/o-hexose Cladinose 2.6-Dideoxy-3-C-methyl-3-O-methyt-L-tibo-hexose Colitose 3.6-DideoXY-l-xy/o-hexose Cymarose 6-0eoxy-3-O-methyt-ribcrhexose 2-Oeoxyribose (dRib) 2-0e0xy·el)lthro-pentose 2-Deoxyglucose (2dGIc) 2-Oeoxy·ambino-hexose Diginose 2,6-Dideoxy-3·().melhyt-~hexose Digitalose 6-Oeoxy-3-CHnethyl·o-gaIactose Digitoxose 2,6·Dideoxy·o-rrbo-hexose· Evalose 6·Deoxy-3-C-melhyt·o-mannose Evemitrose 2.3.6-Trideoxy·3-C-methyl-4-O-methyl-3-nilro-L-ambino-hexose Gentianose p·o-Fructofuranosyl!l-D-glucopyranosyf·(1 .... 6)-a-o·glucopyranoside Gentiobiose 1l-O-Glucopyranosyl-(l-+6j-O-glucose Hamamelose 2-C-(Hydroxymethyl)·o-ribose Inulin (2.... 1)·Il-o·Fructofuranan

lsolevoglucosenone 1.6-Anhydro-2.3-dideoxy~o-g/yl:8ro-hex·2-enopyranos-4-ulose

lsoma~ose a-o-Glucopyranosyl·(I->6)-o-glucose

tsoma~triose a-O-Glucopyranosyl-(I->6)-a-o-glucopyranosyf-(l->6)-o·glucose lsopanose a-O-Glucopyranosyl·(I-+4)-{a-D-gfucopyranosyl-(1 .... 6)I-o-glucose Kojibiose a-o-Glucopyranosyl·(1-+2)-o-g1ucose lactose (lac) jI-o-Galactopyranosyl·(l-+4)-O-glucose lactosamine (lacN) fk>-Galactopyranosyl-(I-+4)-D-gfucosamine Lactosediamine (lacdiN) 2·Amino-2-<1eoxy-fk>-galactopyranosyt·(1-+4)-o-glucosamine laminarabiose jl-o-Glucopyranosyl·(l-+3)-o-glucose

levoglucosan 1.6-Anhyd*Dillucopyranose levoglucosenone 1.6-Anhydr0-3.4-dideoxy·JH>-gIpro-hex-3-enopyranos-2-u1ose

Ma~ose a-o-Glucopyranosyf-(l-+4)-o-gtucose Maminotriose a-o-Galactopyranosyl-(l-+6j-a-o-galactopyranosyl·(1 .... 6)-O-glucose

Melezitose a-o-Glucopyrano$yl-(I-+3J~-o-lructoluranosyf a-o-glucopyranoside Melibiose a-o-Galactopyranosyl-(t->6)-O-glucose Muramic acid (Mur) 2-Amino-3-0-{(R)·I-carboxyethyIJ·2·deoxy-o-glucose Mycarose 2,6-Dideoxy-3·C-methyl-l·rrbo-hexose Mycinose 6·Deoxy-2.3-di·O-melhy!-o-allose 2845

Neuraminic acid (Neul 5-Amino-3,5-dideoxy-D-gI)o-gaIacto-n0n-2-u1osonic acid a-o-GlucopyranosyJ-(l->3)-O-gtucose Nojirimycin 5-Amlno-5-d90XY-Dillucopyranose Noviose 6-0e0xy-5-C-melhyl-4-o-methyl-t..-/yXO'-hexose Oleandrose 2,6-0ide0xy-3-().methyI-t.-anrbitJo.hexose Panose _ a-o-GlucopyranosyI-(l--t6)-a-o-glucopyranos-(l-+4}o-g1ucose Paratose 3.6-Didaoxy-o-rlbo-hexose Planteose Q.o-Galaclopyranosyt.(l~ructofuranosyt a-o-glucopynlnoskfe Primeverose p..o..XyIopynmosyt.(l--t6)-o-g1uoose Raffinose IHl-FructofuranosyI CI-o-galactopyranosyl-(l-i6}a-o-gluoopyranos Rhodinose 2,3,6-Trideoxy-t.-threo-hexose Rutinose a-l.-Rhamnopyranosyl-(l-J6).o-glucose

Sannentose 2,6-Dideoxy-3-~xyIo-hexose Sedoheptulose D-aItJo.Hept-2-uIose Sedoheplulosan 2,7-Anhydro-J!-o-aftro.hept-2-u1opyranose Solatriose a-I.-RhamnopyIanosyI-(1-4)-{l1-o-g1uc:op-(1;3»)oO-g8IacIose Sophorose jk)-Glucopyranosyt-(1-+2).o-gIucose fHl-Fruclofuranosyi a-o-galactopyranosyl-(l-+6)-a.o-galactopyranosyl-(l-+6)-a-o­ glucopyrenoside SII8pIOSe 5-0e0xy-3-C-formyl-L-lyxose Sucrose p-o-Fructofuranosyl a-O-glucopyranoslde (saccharose) u,a-Trehalose a-o-Glucopyranosyt a-o-glucopyranoslde Trehalosamine 2-Amino-2-deoxy-a-o-glucopyranosyl a-o-gIucopyranoside a-o-Glucopyranosyt-(l->3)-o-fructose Tyvelose (Tyv) 3,6-Dideoxy-D-a/l!lbino-hexose UmbeUiferose iW>-Fructofuranosyl a-o-galaclopyranosyl-(l-+2)-a-o-galactopyranoside

(c) trivial names fonned by modificatioD of DOD-Staodard monosaccharide parent names

Acosarnine 3-Amino-2,3.6-trideoxy-l-xyto-hexose Bacilosemlne 2,4-Diamino-2,4,6-trideoxy-o-glucose Daunosemlne 3-Ami1o-2,3.6-trideoXY-l-/yJw-hexose Desosamine 3,4.6-Trideoxy-3-dimethylarnino-D-xyto-hexose Forosamine 2,3,4,6-Tetradeoxy-4-dlmathylamino-o-e/)ItIW-hexose Garosamine 3-Deoxy04-C-methyt--3-methylamino-L-arablnose Kanosamine ~xy-o-glucose Kansosamine 4,8-Oide0xy-3-C-methyl-2-0-rnethy\-L-mannose Mycamino6e 3.6-Dideoxy--3-dimethytamino-D-glucose Mycosamine 3-Amino-3,6-cfIdeoxy-o-rnannose Perosamine 4-Amin0-4.6-

Clu. Amino sugar" Uronic Icidb U10senic acid The sialic acid familY!> {usually as acetamido UrofllJte Ulosonate (N-acctyl) derivative) GJycose Aminodeoxyglycose Glycuronic acid Olyculosonic acid Neuraminic acid (}OH Olycurcmale GlyculosoTlate Sialic acid [Olycosamine] [Ketoglyconic acid]

Glycosyl Aminodeoxyglycosyl Olycosylurcnic acid Olyculosylonic acid [Neuraminosyl]< 0- GI)!co~luronat. Glyculo~IOfUIt. (SiaJosyll' [Glycosaminyl] [GlycuronosylJ

Glycoside Aminodeoxyglycoside Glycosiduronic acid Glyculosidenic acid [Neuraminoside] (}OR GlycosidurcmtJl. Glyculosidonat. [Sialoside J [Glycosarninide] [Glycuronide]

Glycosidase Aminodeoxyglycosidase Glycosidurcnase Glyculosidonase [Neuraminidase]

Glycosyltransferasc Aminodeo

"The biochemical usage is widely established in the literature. hntc biochemical usage implies the parents ',Iycuronose', 'sialose'. and 'neuraminose'. "NeW'lllllinyl' and 'slalyl' haye been used, but are likely to be interpreted as referring to acyl groups; the terms given are more consistent with the terms used for glycosides Subject Index

Acetamido group 1543 Anomerization 785 Acids 877 Antiadhesives 2393 Acid-washed molecular sieves 1543 Antibiotic 2305,2471 Action patterns 1905 - resistance 2393 Acylation 467 Antifreeze glycoproteins 2289 Addition reactions 253 Antigenic determinants, GPI Adhesion domains 1905 anchors 2253 ADPGlc 75 anti-HIVactivity 365 Affinity and mechanism-based Antitumor 2441 inhibitors 1905 - and antimicrobial drugs 2393 Ajugose 1661 Arabinogalactan 2005 Alcoholoxidation 195 Archaebacteria 2107 Alditols 501,877 Armed/disarmed 535 Aldol reactions 305,691 Aromatization 785 Aldolase 907 Aryl glycosides 1497 Aldonolactones 501 Asialoglycoprotein receptor 1779 Aldose 501,583,877 ATP 75 Alginates 75 Auxiliary group 1543 Alkaloid glycosides 2471 Azasugar 907 Alkylation 467 2-Azido-2-deoxy-glycosyl Allylic rearrangement 907 nitrates 1497 Allyloxycarbonyl 117 Azido group reduction 1543 Amadori 385 Azidonitration 195, 907 Amino sugars 885,907,1023,1215 - Bacterial adhesion 1543 -, N-protection 1543 - of glycals 1497 1,6-Anhydrohexose 1497 Anhydro sugars 627,885 Base-transfer reaction 673 Anhydronucleosides 291 Benzyl 117 Anomeric 785 Benzylidene 117 - acetate 1497 Bicyclic sugar mimic 2541 - center 467,501 Bioengineering 1905 - chloride 1497 Biological - control 551 - activity 1993 effect 3,1497 - properties 53 - protecting group 1497,1543 Biosensors 1325 2848

Biosynthesis 1695,2149 1,2-cis-Linkages 1497 Blood group antigens 1497,2289 Classification schemes 1905 Blood-brain barrier 2355 C-Linked glycosyl amino acids 2679 Branched-chain sugars 305,885,1215 C-linked oligo saccharides 2679 Brigl's anhydride 1497 Cold anhydrous liquid hydrogen 2-Bromo-2-deoxy glycoside 1497 fluoride 1497 a-Bromoenamines 1497 Combinatorial chemistry 1621 Complex oligo saccharides 1883 CAN 117 Conformation 2305 Cancer therapy 1325 - Chair 3 Cancer vaccine 1543 Contraction 417 Carageenans 75 Coupling Carbasugars 885 - constants 3 Carbistrin A 1175 - reactions 2441 Carbohydrate 749,1817,2595 Crystallization 63 - analogues 2533 Ctmp 117 - medicinal chemistry 2725 Curdlan 1993 - -binding modules 1905 Cyclic bromonium ion 535 Catalytic domains 1905 Cyclitols 877,2595 Caveolae 1695 Cyclization 785 C-disaccharides 1445 Cyclodextrin 1993 Cee 117 Cell wall 1865 DNA 75 Cellulose 75 DATE 117 2107 DDQ 117 C-Glycosides 691 De novo synthesis 1023 C-Glycosyl compounds 2679 Degradation 385, 785 Chain extension 305,691 DEIPS 117 Chemical properties 53,1883 2-Deoxy-a-glycosides 1497 Chemoenzymatic 2305 2-Deoxy glycosides 1497 - synthesis 907 2-Deoxy-2-iodo-a-D-manno 1497 Chiral pool 1175 2-Deoxy-2-iodo-~-D- Chitin 1993 glycopyranoside 1497 1993 2-Deoxy-2-oximo glycosides 1497 a-Chloroenamines 1497 Deoxy sugars 885,907,1215,2393 1-Chloromethyl-4-fluoro-1 ,4-diazoni- Deoxygenation 501 abicyclo [2.2.2] octane Derivation from naturally abundant bis( tetrafluoroborate) 1497 carbohydrates 907 Chromatography 63 Derivatization 63 Chromoprotein 2441 Descending 785 Ciceritol 1661 Desulfation 1895 1,2-cis-a 1497 1993 1,2-cis-a-Glycoside synthesis 1497 D-Fructose 75 1,2-cis-~ 1497 D-Glucal triacetate 1497 1,2-cis-Galactosylations 1543 D-Glucitol 75 1,2-cis-Glycosides 1497 D-Glucose 75 Subject Index 2849

D-Glucuronic acid 75 Expansion 417 Diacylglycerol 2107 - ethers 2083 Fagopyritol 1661 - esters 2083 Ferrier 785 Diagnosis of malignant disease 1325 - reaction 1695,2595 Dianhydro sugars 627 - rearrangement(s) 365 (Dibromomethyl) benzoyl 117 Fischer glycosylation 1497 Dichloroacetamido protecting Fisher glycosidation 467 group 1497 FK-506 1175 Dichloromethyl methyl ether 1497 Flagpole steric interaction 1497 Dihydroxylation 195,907 Flavonoid glycosides 2471 Dimethylthexylsilyl 117 a-Fluoroenamines 1497 2,3-Dinitrophenyl group 1497 Fluoro sugars 885 Diol acceptor 1543 Fmoc 117 Disaccharide 3, 1445 Formose reaction 1023 - monomer 1465 Fpmp 117 - thioglycoside 1497 Functional mime tics 2725 Disialic acid donor 1543 Furanose oligo saccharides 2005 Dispiroketal 117 D-Mannose 75 GAG, Galabiose 1543 D-Mannuronic acid 75 Galal-4Gal 1543 DMTr 117 Galal-4Xyl 1543 DNA 75 Galactinol 1661 DNA binding 2441 - synthase 1661 Dnseoc 117 Galactopyranosyl acceptors 1543 Double bond 417 Galactopyranosyl donors 1543 Drug design 2005 a-Galactosidase 1661 DTBS 117 Galactosylgloboside 1543 Galactosyloligosaccharides 1661 Elaiophilin 1175 Gal~I-3GaINPhth 1543 Electron transfer 231 Gal~I-4Xyl 1543 Electrophoresis 63 Gal~I-4Xyl~I-4Cer 1543 Enediyne 2441 Galectin 1779 Energy 1865 GD3- 1543 Enterococci 2107 GD3-lactam 1543 Enzymatic GD3-lactone 1543 - polyaddition 1465 Globoseries glycolipids 1543 - polycondensation 1465 1543 Enzymes 1325 Globotriosyl ceramide 1543 Epoxidation 291 Gluconeogenesis 1215 Epoxide 231,627 Glucosan 627 Epoxy 417 Glycal 583,749,1497 Erythromycins 1175 Glycan 1865 , Fabry's disease 1543 Glycanase 1465 Eubacteria 2107 Glyceroglycolipid 2107 Exopolysaccharide 1865 Glycerol 75 2850

- phosphate 2107 GPI 1695 Glycitols 1215 GTlaa 2107 1497,2393 Guanidine/guanidinium nitrate-in- Glycoforms 2253 duced de-O-acetylation 1543 75 Glycoglycerolipid 2107 Halichondrin B 1175 Glycolipids 2083,2097,2149 Halide ion exchange method 1497 Glycolysis 1215 253 Glycomimetics 2725 Helferich catalyst 1497 Glyconic acids 1215 Hemiacetals 1497 Glycopeptide 1497,2253,2289 Heparan sulfate 1993 - antibiotics 2253 Heparin 1993 - conformation 2289 1023 Glycopeptidolipids 2083 Herbimycins 1175 Glycopolymer 1993 Hexadecasaccharide hapten of Glycoproteins 75,1589,2253,2289, Shigella 1497 2355 Hexoses 1023 75,1543,1865, High throughput synthesis 1621 1895,1993 Higher anhydrosugars 291 Glycosan 627 Hopanoids 2083,2097 Glycosidase inhibitor 2541 Hormones 2355 Glycoside 2471 H-phosphonate 117,1695 - hydrolysis 467 Human blood group antigenic ~-Glycosides 673 determinants 1497 Glycosidic bond 1497 Hyaluronic acid 1993 a-Glycosidic linkages 1497 Hydride reduction 231 2083,2107,2183 Hydrogen bromide in acetic acid 1497 Glycosyl Hydrolases, Lyases 1905 - acceptor 1497,1543 Hydrolysis 785 - donor 673,1543 Hydroxymethyl 3 - fluoride 583,1465,1497,1543 Hydroxy-protecting 117 - iodides 1497 2-Hydroxy thioglycosides 1497 - lithium 2679 - phosphate 583 Imino sugars 2541 - phosphite 583 Iminofuranose 2541 - radical 2679 Iminopyranose 2541 - 2679 Inflammation 1543 - transferases 1905 Inflammatory response 2305 - trichloroacetimidate 583 Infrared spectroscopy 885 Glycosylation 535,627,673,1589,2107 Inositol resolution 1695 Glycosylation mechanism 1543 Insulin 1695 Glycosylphosphatidylinositol 1695 Intramolecular [3+2] Glycosyltransferases 2005 cycloaddition 2595 Glycuronic acids 1215 117 GM2-lactone 1543 2-Isobutenyl glycosides 551 GM3-lactam 1543 Isopropenyl glycosides 551 Subject Index 2851

Isopropylidene 117 Mimics 2533 Mismatched pair 1497 Ketone reduction 195 MMTr 117 Ketoses 877 Molecular Koenigs-Knorr reaction 1497 - dynamics 3 - mechanics 3 Lactacystin ll75 - recognition 1817,2393 Lectin 1779,2289 Monosaccharide 3,749,877,885,907, 1993 1023 Levoglucosan 627 - complexes l325 Levoglucosenone 627 - mime tics l325 Levulinyl ll7 Mox ll7 Lewis - a blood group Mthp ll7 determinant 1497 Mucins 2253 Lewis acid catalysis 1497 Muramic acid 75 Lewis acids 1497 Mutarotation 467 L-Guluronic acid 75 Mycobacteria 2005 Library 1621 Mycolic acid 2107 L-Iduronic acid 75 myo-Inositol 1661 1,3-Linked disaccharide 1497 1,6-Linked disaccharide 1497 N ,N ,N' ,N' -Tetramethylphosphor- Linked sugars 2725 amidates 1543 LipidA 2107 N,N-Diacetyl group 1543 Lipoarabinomannan 2005 N,N-Dibenzylamino group 1543 Lipoglycans 2083 N-Acetyl group 1543 Lipophosphoglycan 2083 N-Acetyl-D-galactosamine 75 Lipopolysaccharides 2083,2097,2107, N-Acetyl-D-glucosamine 75 2183 N-Acetyllactosamine 1543 Lipoteichoic acids 2083,2097,2107 N-Acylsphingosine 2107 Long-range neighboring group Natural products 2471 participation 1497 NBS-mediated activation 673 Lysosomes 2149 Neighboring group participation 1497 Neu5Aca2-3Gal 1543 Macrophage mannose receptor 1779 Neu5Aca2-3Galpl-4XylplCer 1543 Maillard reaction 385, 785 Neu5Aca2-8Neu5Ac 1543 Mannose 1589 New generations of glycosidase Mannose binding protein 1779 inhibitors 2595 Mannose-6-phosphate receptor 1779 N- 2253 Mass spectrometry 885 Nitrile effect 1543 Mechanism of action 1905 Nitro sugars 885,2679 Medical application 1993 Nitrobenzyl 117 Metabolic engineering l325 Nitrogen 253 Methoxybenzyl ll7 NMPEC 117 Methylene 117 NMR 3 Microheterogeneity 2253 NOE 3 Mimetic 2305,2533 Non-anomeric 385,417 2852

Nonspecific and regiospecific Peptidoglycan 2253 sulfation 1895 Phase-trans fer-catalyzed 0- N-Pent-4-enoyl group 1543 benzylation 1543 n-Pentenyl glycoside 535,551,1695 Phenolic glycolipids 2083 NPEOC 117 Phenyl sulfoxide 1543 NPMOC 117 Phosphate migration 117 Nucleophilic substitutions 253 Phosphates 877 Nucleoside diphospho-monosaccha- Phosphatidic acid 2107 ride-dependent synthases 1905 Phosphitylation 117 Nucleotide diphosphates 1497 Phosphoinositol glycan 1695 Phospholipase 1695 2-0-Acetyl-l,6-anhydrogalactose 1497 Phosphonate 117 1023 Phosphoramidite 117, 1695 O-Glycans 2253 Phosphorus 253 O-Glycosidation 583 Phosphorylases 1905 Olefin hydrogenation 195 Phosphorylation 117 Oligomer 1435 Photolysis 117 Oligomerization 1779 Photolytic deoxygenation 231 Oligosaccharide 3,1435,1445,1465, Photosynthesis 75,1215 2441 Physical properties 53 - synthesis 535,1497 Physicochemical properties 2097 O-linked glycopeptides 2355 Pinitol 1661 Ononitol 1661 - galactoside 1661 - galactoside 1661 Piperidines and bicyclic Opiates, transport 2355 homologs 2541 Organometallic compounds 305 Pivaloylaminobenzyl 117 Orthoester 117,1497,1543 Pix 117 - Oxazolines 1497 Plant glycolipids 2183 1,2-0rthoester 1695 Planteose 1661 Orthogonal glycosylation 1497 p-Methoxybenzyl ether 1497 O-Specific antigen 1497 p-Methoxybenzylidene 1497 Oxalyl chloride 1497 p-Methoxyphenyl glycosides 1497 Oxazine 1497 Polyhydroxylated alkaloids: Oxazolines 1543 pyrrolidines 2541 Oxidation 501,907,1883 Polymer-supported Oxidative deblocking 117 - solution synthesis 1621 Oxidative pentose phosphate - synthesis 1621 pathway 1215 Polynucleotides 75 Oxocarbonium ion 1497 Polyprenol diphospho-oligosaccharide- dependentsynthases 1905 Parasites 2183 Polysaccharide 1465.1865,1993 Parvovirus B19 1543 - sulfates 1883 P-blood group system 1543 Polyvalency 1817 Pentitols 1023 Prevost reaction 1497 1023 Protecting groups 467 Pentraxin 1779 Protein 1325 Subject Index 2853

- activity 2289 Silyl - sorting 1695 - migration 117 - stability 2289 - protecting groups 1497 Proteinaceous inhibitors 1905 SmI2-mediated chemistry 2595 Protein-polysaccharide 1865 Solid phase synthesis 1621,2725 Proteoglycan 1865,2253 Solid-phase 2305 PSEC 117 Spaced sugars 2725 Purification 63 Spacers 535 Pyruvate 117 Specificity and specificity-determining structures 1905 Radical 385 Sphingoglycolipid 2107 - cydization 2595,2679 2149 - deoxygenation 231 Sphingolipid activator proteins 2149 Raffinose 1661 SSEA-4 2107 Raffinose synthase 1661 Stachyose 1661 Rare sugar 907 Stachyose synthase 1661 Rearrangement 291,417,785 Starch 75 Receptors 1325,1543 stereoselective 1589 Reduction 501,907 - synthesis 907 Reductive ring-opening 117 Steroid glycosides 2471 Ribitol 75 Steryl glycosides 2083 Ring heteroatom 253 Streptococci 2107 Ring-contraction 785 Structure elucidation 1695 Ring-expansion 785 Structure-activity relations 247l Ring-opening 785 Structure-function relationships 1905 RNA 75 Sucrose 1497,1661 Sugar 877 Saccharide-peptide hybrids 2725 - amino acids 2725 Samarium 231 - carboxylate 907 Schizophylan 1993 - organometallic 2679 SEE 117 - oxazoline 1465 Selectfiuor 1497 - oxiranes 291 Selectin 1779,2289 - phosphates 75 Selenophenyl neighboring Sulfated glycolipids 2083 groups 1497 Sulfation patterns 1895 SEM 117 Sulfoxides 1497 Sesamose 1661 Sulfur 253 Sialic acid 1215,2107 Synthesis 643,749 Sialyl Lewisx 2725 - of complex oligo saccharides 1497 Sialylation 2107 Synthetic polysaccharide 1993 Siglec 1779 Signal transduction 1695 Tautomycin 1175 Tay-Sachs ganglioside 1497 - on alumina 1497 TBDMS 117 - salt promoters 1497 TBDPS 117 - silicate 1497 Teichoic acid 75,1497 2854

Tetraalkylammonium salt 1497 Trehalose 2107 1023 Trehalose dimycolate 2107 4-Thioaldofuranoses 2663 Trehalose-containing lipo- 5-Thioaldopyranoses 2663 oligosaccharides 2083 6-Thioaldoseptanoses 2663 Tributyltin hydride 231 Thiocarbonyl ester 231 Trichloroacetamide 1497 Thiodisaccharides 1445 2,2,2-Trichloroacetimidate 1695 Thioglycoside 551,627,643,1497 2,2,2-Trichloroethoxycarbonylamino Thioglycosylation 643 group 1543 5-Thioketofuranoses 2663 Trichloroethyl glycoside 1497 6-Thioketopyranoses 2663 Trichloroethylidene 117 4'-Thionucleosides 2663 Trimethylsilyl chloride 1497 Thiophenyl ether 1497 Trimethylsilyl ethyl 1497 Thiosaccharides 643 2-(Trimethylsilyl)ethyl glycoside 1543 Thiosugars 885, 2663 1023 THP 117 Trisaccharide thioglycoside 1497 TIPDS 117 Trityl 117 TIPS 117 Troc 117 TMSEC 117 Tuberculosis 2005 Tosylate 231 total synthesis 365 UDPGlc 75 1,2-trans 1497 Umbelliferose 1661 1,2-trans-a 1497 unsaturated nucleosides 365 1,2-trans-a-Glycosidic linkages 1497 1,2-trans-~-Glycosidic linkages 1497 Vaccine, antigen 2305 trans-Glycosides 1497 Verbascose 1661 1,2-trans-Glycosides 1497 Vilsmeyer chlorinating reagent 1497 trans-Glycosyl halides 1497 Vitamin glycosides 2471 trans rule, Acyloxonium cation 1497 Transition-state analogue Wittig-Horner reaction 691 inhibitors 1905 Wittig-type reactions 365 Transporters 1325