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Versatile Building Blocks from Disaccharides: Glycosylated 5-Hydroxymethylfurfuralsi Dierk Martin and Frieder W

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Versatile Building Blocks from Disaccharides: Glycosylated 5-Hydroxymethylfurfuralsi Dierk Martin and Frieder W Tetrahedron: Asymmetry 17 (2006) 756–762 Versatile building blocks from disaccharides: glycosylated 5-hydroxymethylfurfuralsI Dierk Martin and Frieder W. Lichtenthaler* Clemens-Scho¨pf-Institut fu¨r Organische Chemie und Biochemie, Technische Universita¨t Darmstadt, Petersenstraße 22, D-64287 Darmstadt, Germany Received 10 December 2005; accepted 19 December 2005 Available online 15 March 2006 Dedicated to Professor Klaus Buchholz on the occasion of his 65th birthday Abstract—A practical protocol for the elaboration of O-glycosyl-HMF’s from glycosyl-(1!6)-glucoses is reported, the two steps involving aluminate-promoted isomerization to the respective 6-O-glycosyl-fructoses and subsequent selective dehydration of the fructose portion. Accordingly, melibiose, gentiobiose, and primeverose are converted into the corresponding 2-uloses and, then, into a-GalMF 11, b-GMF 12, and b-XylMF 13. Pt/C-catalyzed oxidation with oxygen in NaOH at 25 °C efficiently generated the respec- tive furoic acids from a-GalMF and a-GMF, whilst Pt/O2 in water at 50 °C also oxidizes the primary OH to give the dicarboxylic acids 15 and 17–key building blocks for the generation of novel types of polyesters and polyamides. Ó 2006 Elsevier Ltd. All rights reserved. 1. Introduction HO O As carbohydrates represent 75% of the annually renew- O HOOC O COOH H able biomass, their utilization for the generation of 1 2 chemicals and materials that eventually replace those from fossil resources is a major challenge for green 2,3 OH chemistry. This entails the development of efficient O methodologies for the simultaneous reduction of their HO oxygen content and introduction of C@C and C@O HO HO functionality toward industrially viable building blocks. O O Furan-type heterocycles are prototypes of such chemi- O 3 cals: furfural, already produced on an industrial scale H from biomass-derived xylose,4 5-hydroxymethylfurfural 1 (HMF),5 for which a pilot plant process for produc- 6 tion from D-fructose or inulin is available, and which—in the form of its oxidation product furan-2,5- 8 dicarboxylic acid 2—is considered to be one of the top derived isomaltulose —has gained interest as a building 9 12 biomass-derived chemicals deserving further exploita- block for a novel type of liquid crystals, as well as for a tion.7 variety of hydrophilic pyrroles, pyridazines, and diazepi- nones,10 we opted to investigate the preparation of Since a hydrophilic version of HMF, 5-a-D-glucosyl- O-glycosylated HMF’s with other sugar portions and oxymethyl-furfural 3 (a-GMF)—accessible from sucrose- anomeric configurations—preferably not by glycosyla- tion of HMF, as the yields obtainable are modest.11 This has been attributed to the electron-withdrawing effect of q Part 38 of the series, Sugar-Derived Building Blocks. For Part 37, see the aldehyde moiety decreasing the nucleophilicity of the 11 Ref. 1. hydroxyl group, yet is more likely due to the substan- 12 * Corresponding author. Fax: +49 6151 166674; e-mail: lichtentha- tial formation of the known bis-HMF-ether 4 under a [email protected] variety of glycosylation conditions.13 0957-4166/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.tetasy.2005.12.010 D. Martin, F. W. Lichtenthaler / Tetrahedron: Asymmetry 17 (2006) 756–762 757 OH O O O 4 O O HO OH 5 R = α-D-Gal (melibiose) 6 R = β- D-Glc (gentiobiose) H H RO 7 R = β- D-Xyl (primeverose) OOH Hence, the approach followed for the generation of a- GMF—selective dehydration of the fructose portion of isomaltulose under conditions that retain the intergly- 75-80% 1. NaAl(OH)4 8 cosidic linkage —was applied to other glycosyl-(1!6)- 2. H+ fructoses, namely melibiulose 8, gentiobiulose 9, and HO OH 8 R = α-D-Gal (melibiulose) primeverulose 10. Accordingly, we herein report their 9 R = β- D-Glc (gentiobiulose) efficient preparation from the respective glycosyl- 10 R = β- D-Xyl (primeverulose) (1!6)-glucoses, their conversion into a-GalMF 11, RO O OH b-GMF 12, and b-XylMF 13, and some follow-up OH reactions. 60% H+ resin, DMSO 11 R = α- D-Gal (α-GalMF) 2. Results and discussion 12 R = β- D-Glc (β-GMF) 13 R = β- D-Xyl (β-XylMF) 2.1. Aluminate-mediated isomerizations of 6-O-glycosyl- RO O glucoses O H Unlike a-D-glucosyl-(1!6)-D-fructose (isomaltulose), O which is produced on a ton scale from sucrose by bacte- Scheme 1. Sodium aluminate-mediated isomerization of 6- -glycos- 14 ylated glucoses to their fructose analogs (5–7!8–10) and their rial O-2!O-6-transglucosylation, other 6-O-glycosyl- dehydration to the respective 5-O-glycosylated HMFs 11–13. ated fructoses, such as melibiulose 8, gentiobiulose 9, and primeverulose 10, although known,15–18 are consid- 19 erably less accessible. The better accessibility of the aluminate with D-glucose and D-fructose have been respective 6-O-glycosyl-glucoses melibiose 5,20 gentio- prepared30,31 and that the association constant of the 21 22 biose 6, and primeverose 7, meant that a procedure D-fructose–aluminate complex is 5–10 times higher than 31 had to be sought for effectively isomerizing their termi- the one formed from D-glucose. The higher affinity of nal glucose unit to fructose. Of the various methods D-fructose to aluminate was also inferred from its pro- evaluated,23 the one most suitable was found to be one nouncedly larger retentivity on columns with resins in adapted from the aluminate-promoted conversion malt- the aluminate form, such that glucose/fructose mixtures ose into maltulose24 (70% of crystalline product25), and can be readily separated due to fast elution of the less lactose into lactulose (85%),26 which in turn relied on strongly complexed glucose part.30,31 an earlier patent for a glucose!fructose conversion (67%).27 The protocol simply involves heating of As of now, structural characterizations of these reducing an aqueous solution of the glycosyl-glucoses 5–7 sugar/aluminate complexes are not available. As it is with sodium aluminate (4 h, 45 °C) the respective generally accepted, however, that the first step in alkali- reaction mixtures comprising about 85–90% of the promoted transformation of aldoses is the formation desired glycosyl-fructoses 8–10 (HPLC) aside the educts, of a 1,2-enediolate23,28 through abstraction of H-2 from their component sugars and D-fructose (1–2% each), the aldehydro form of the sugar, an enediol–aluminate yet—notably—only trace amounts of the respective complex of type I (Scheme 2) appears to be the most glycosyl-mannoses. plausible intermediate in the D-glucose!D-fructose conversion. The subsequent step then can be conjectured Compared with the large variety of reactions induced on as a cyclization analogous to the common hemiacetal- exposure of aldoses to alkali—C-2-epimerization,23 rear- ization, which can occur by attack of either O-6 or of rangement to the ketose,23 retro-aldolization with subse- O-5 at the C-2 of the enediolate, thereby elaborating quent recombination of the fragments,28 and formation the spiro-1,2-aluminate complexes of fructose in the of saccharinic acids29—the aluminate-mediated treat- pyranose (IIa) and furanose forms (IIb), respectively. ment of the 6-O-glycosyl-glucoses 5–7 takes a distinctly As these transformations, in principle, are reversible, a more uniform course: rearrangement to the respective shift of the equilibria Ia M IIa and Ib M IIb to the fruc- glycosyl-fructoses 8–10 is highly preferred (85–90%), tose side must be operative to account for the high fruc- such that the glucose!fructose conversion is the tose yields obtained on acidification—a reasonable predominant if not exclusive reaction path followed. assumption as aluminate stabilizes fructose distinctly stronger than the isomeric glucose.30,32 A mechanism capable of explaining this preference obvi- ously has to rely on aluminate complexes of the two Of the two pathways delineated in Scheme 2, there are sugars and/or the respective reaction intermediates as no arguments for a preference, as of now. That aqueous differences in their stabilities are likely to shift the equi- solutions of D-fructose mainly contain the b-pyranoid libria involved to the fructose side. Evidence toward this tautomer (73% at 25 °C33) may accentuate the fructo- end may be drawn from the fact that 1:1 complexes of pyranose complex IIa, yet its furanoid counterpart IIb 758 D. Martin, F. W. Lichtenthaler / Tetrahedron: Asymmetry 17 (2006) 756–762 appears equally important as conversion of the 6-O- ing in an anhydrous DMSO solution in the presence of a blocked glucoses 5–7 to their respective fructoses 8–10 dry, strongly acidic ion exchange resin for 3 h at can only proceed through furanose intermediates. 120 °C8—were applied. Mixtures of the correspon- ding glycosyl-HMF’s (ca. 70–75%), dimeric glycosyl- fructoses (5–10%), HMF, and the respective aldose OH OH (5%) were obtained, which were readily separated to H O OH give a-GalMF 11, b-GMF 12, and b-XylMF 13 in crys- HO HO HO OH HO talline form and in yields of around 60% (Scheme 1). HO From a practical point of view though, these glycosyl- HO O HMF’s are more readily prepared from the respective D-Glucose NaAl(OH) glycosyl-(1!6)-glucoses 5–7, as the two steps 4 involved—base-promoted glucose!fructose isomeriza- OH tion and acid-induced dehydration of the crude glycosyl-fructoses 8–10—can be readily combined into H H HO O O a continuous operation with overall yields also in the HO HO HO HO 60% range.
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