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Synthetic Transformations of a 2,3-Unsaturated Sugar Leading to Novel Sugars

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Synthetic Transformations of a 2,3-Unsaturated Sugar Leading to Novel Sugars This dissertation has been microfilmed exactly as received 70-6711 ALBANO, Ester Laigo, 1942- SYNTHETIC TRANSFORMATIONS OF A 2,3-UNSATURATED SUGAR LEADING TO NOVEL SUGARS. The Ohio State University, Ph.D., 1969 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan SYNTHETIC TRANSFORMATIONS OF A 2,3-UNSATURATED SUGAR LEADING TO NOVEL SUGARS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University ■ Ester Laigo Albano, B.S. The Ohio S tate U niversity 1969 Approved by Adviser Department of Chemistry ACKNOWLEDGMENT The author expresses her gratitude and appreciation to Professor Derek Horton for his guidance and encouragement during this investigation. The author also thanks the United States Department of Agriculture Grants No,. 12-14-100-7208 (71) and 12-14-100-9201 (71) (O.S.U.R.F. Projects 1827 and 2573)? National Institutes of Health, Public Health Service, Department of Health, Education and Welfare, Grant No. GM-11976-04 (O.S.U.R.F. Project 1820)} the Stauffer Chemical Company; and the International Rice Research Institute for financial support. ii VITA March 18-, 1942 . Born - Dingras, Ilocos N orte, Philippines 1963 ....................................... • B.S., University of the Philippines (cum laude) 1963-I 964 • • • . • Research Assistant, International Rice Research Institute, Philippines 1964-I 966 ........ Teaching Assistant, Department of Chemistry, The Ohio S ta te U niversity, Columbus, Ohio 1966-1969 ................................. Research Associate, Department of Chemistry, The Ohio S tate U niversity, Columbus, Ohio , PUBLICATIONS 1. "Variability in Protein Content, Amylose Content, and Alkali Digestibility of Rice Varieties in Asia." B. 0. Juliano, E. L. Albano, and G. B. Cagampang, Philippine A g ric u ltu rist, £ 8 * 234 (1965). 2. "Varietal Differences in Physicochemical Properties of Rice Starch and I ts F ractio n s." A. C. ReyeB, E. L. Albano, V. P. Briones, and B. 0. Juliano, J. Agr. Food Chem., l£j 438 (l%5). 3* "Synthesis and Reactions of UnBaturated Sugars. IV. Methyl 4 ,6-O-Benzylidene- 0-D-erythro-hex-2-enonyranoside and Its Hydrolysis by Acid." E. L. Albino, D. Horton, and T. Tsuchiya, Carbohyd. Res., 2, 349 (1966). 4* "Addition Reactions of a 2,3-Unsaturated Sugar." E. L. Albano, D. Horton, and J. H. Lauterbach, Chem. Commun., 357 (1968). 5. "Synthesis and Reactions of Unsaturated Sugars. IX. Addition Reaotions of Methyl 4, 6-0-Benzylidene- 2, 3-dideoxy-a-D- erythro-hex-2-enopvranoside." E. L. Albano, P. Horton, and JT H. Lauterbach, Carbohyd. Res., % 149 (1969). v FIELD OF STUDY Major Fields Organic Chemistry ' iii CONTENTS Page ACKNOWLEDGMENT................................. .................................................... VITA ....................................................................................................... i i i LIST OP TABLES . ........................................................................... v i LIST OP FIGURES...................................................................................... v i i LIST OF CHARTS..................................................................... v i i i INTRODUCTION ................................................................. X HISTORY ......................................................... 6 Synthesis of Unsaturated Sugars ........................ 6 KLeotrophilio Additions to Alkenes ........ 15 Sugar Components of A ntibiotics ........................ 32 Mass S p ectro m etry ................................................. 37 STATEMENT OF THE PROBLEM . .......................................................... 39 DISCUSSION........................................ 40 Synthesis of Methyl 4,6-0-Benzylidene-2,3- dideoxy-a-D-arythro"hex- 2-enr>pvrano 3ide by the Corey-Winter Olefin Synthesis ...... 40 Attempts to Prepare Methyl 4j6-0-Benzylidene- 2r3-dideoxy-a-D-erythro-hex-2-ennpvrannside from Methyl A,5-0-Benzylidene-a-D-mannopyrano- side by the Tipson-Cohen ProcedifFe and by Reaction with Potassium Ethylxanthate ...... 44 Addition Reactions of the 2,3-Olefin . • .... • 45 Synthesis of Methyl 2,3,6-Trideoxy-a-D- erythro-hexopvranoside (Methyl a- = amicetoside) .... .-. .. .. ... .. iv CONTENTS (Continued) Page Synthesis of 2,3,4,6-Tetradeoxy-4-dimethyl- amino-D-erythro-hexose (Forosamine) and I ts threo Epimer ................................ 73 Mass Spectrometry of Benzylidene Acetals .................... g 2 EXPERIMENTAL . ............................................... 87 LIST OF TABLSS Table . pafie * * I 1. Coupling Constants of Methyl 4,6,-(2-benzylIdene- a-D-hexopyranosides .................................................... 49 2. Major Peaks in the Mass Spectra of Some Benzylidene Acetals ••• 84 3. Chemical Shifts of Acetoxy, Benzoyl, Benzyl, Cyclopropyl, Methoxyl, and Phenyl Protons (Compounds 1, 2, 37, 41-48) . • . ........................ 126 w m ivw w m Mar 4* Chemical Shifts of Ring Protons (Compounds 1, 2, 37, 41-48) . ................................... ~. 7 . 127 MMM MM MM 5. First-Order Coupling Constants for Ring Protons (Compounds 1. 2, 41-48) 128 m M ■ MM war 6. * Chemical Shifts of Acetoxy, Aryl, Benzyl, • Methoxyl, OH, and NH Protons (Compounds 51-59) ..••••• ................. .... 129 ( MM WW 7. Chemical Shifts of Ring and Aryl Protons (Compounds 51-59)MM MM . • 130 8 . First-Order Coupling Constants for Ring and Aryl Protons (Compounds 5 1 - 5 9 )......................... 131 MM MM 9. Chemical Shifts of Aryl, Methoxyl, HMe2, OH and NH Protons (Compounds 34, 60-53, 66-68 ) . ... ..... ."7 ."7 7“..................... 132 MM MM 10. Chemical Shifts of Ring Protons (Compounds 34, 60-63, 6 6 - 6 8 ) ................................................ 1 3 3 MM ' MM MM MM 'M M ^ 11. First-Order Coupling Constants for Ring and Aryl Protons (Compounds 34, 60-63,6 6 - 6 8 ) . • . 13/ MM 9 MM MM 9 MM MM 12. Mass Spectra of Some Benzylidene Acetals . , ,'.*•■ 135 13. Metastable-Ion Peaks for nH-ruptureM ..... 3.37 vi ■ LIST OF FIGURES Figure Page 1. The partial n.m.r, spectrum’of methyl 4,6-0- benzylidene- 2 ,3-dibromo- 2 ,3-dideoxy-a-D- altropyranoside at 100 MHz .....................“..... 48 2* The partial n.m.r. spectrum of methyl 4,6-di- 0-ao ety l- 2 ,3-dibromo- 2 ,3-dideoxy-a-D- eltropyr&noside at 100 MHz . ^ . 51 3. The partial n.m.r, spectrum of methyl 4-O-kenzoyl- 2 ,3 ,6-tribrom o -2 ,3 ,6-trideoxy-a-D-altro- pyranoside at 100 MHz .................~. ................. 53 4. The partial n.m.r. spectrum of methyl 4,6-0- benzylidene-2-bromo-2 f 3 -dideoxy-a-p-threo- hex-3-enopyranoside at 100 MHz . .“. 55 5. The partial n.m.r. spectrum of methyl 2-0- acetyl-4,6-Q-behzylidene-3-bromo-3-deoxy- o-D-altropyranoside a t 100 M H z ............................... 58 6. The partial n.m.r. spectrum of methyl 3-0- ac ety l- 4 »6-Q-benzylidene- 2-bromo- 2-de oxy- . a-D-glucopyranoside at 100 MHz ................................. 60 7. The partial n.m.r. spectrum of methyl 2-0- acetyl-4.-fi-benzoyl-3,6-^dibr6mo-3,6- . ~ dideoxy - a -p-altropyranoside at 100 MHz .... 61 8 . The n.m.r. spectrum of methyl 2,3,6-trideoxy- o-D-plycero-hexopyrano 3id -4-ulose at . 100 MHZ . * . * . 77 9. The n.m.r. spectrum of methyl 2,3,6-trideoxy- 3 .3-dideut er io- g -D-elvcer o-hexnpvr an ns i d - 4-ulose a t 100 MIS . ..... 78 LIST OF CHARTS Chart Page I . Synthesis of Amicetose . .............................................. 33 II. Synthesis of Methyl 4 , 6- 0-benzylidene- 2 r3-dideoxy-ct-D-erythro-hex-2- enopyranoslde “ ...................................................... 41 III. Bromination of Methyl 4,6-0-benzylidene- 2 T3-dideoxy-a-D-erythro-hex-2- enopyranoside ~ ................................................................. 46 IV, Acetyl Hypobromite Addition to Methyl 4,6-0- benzylldene-2.3-dideoxy-a-D-erythro-hex- 2-enopyranoside . .= . ......... 57 V. Reaction of the 2,3-Olefin with Carbenoid and Nitrene-like Reagents, Nitrosyl Chloride, and Mercuric A cetate .................................................... 64 VI. Synthesis of Methyl 2,3,6-Trideoxy-a-D- erythro-hexopvranos id e ................... 7 ..... • 68 VII. Characterization of Methyl 2,3,6-Trideoxy- ft-D-ervthro-hexopyranoside ....................................... 69 VIII. Synthesis and Reactions of Methyl 2,3,6- Trldeoxy-a-D-glvcero-hexoPvrannsld-4- ulose . 7 ... • • . ... .. • . 74 IX. Synthesis of 2,3,4,6-T.etradeoxyr4~dimethyl- amino-D-erythro-hexose and I t s Threo Epimer” . ....... ......................... ...... 75 X. Benzylidene Ac etals Used in the Mass Spectral Study . , . 63 v i l i INTRODUCTION Naturally occurring carbohydrates provide a rich source for different kinds of organic compounds that can be of technological and biological importance. Carbohydrates are the basis of various kinds of industries; food and food products, textiles, starch, and starch products and, to a limited extent, general chemicals and pharmaceuticals. Aside from being inexpensive as starting materials, carbohydrates provide access to various series of stereoohemically related compounds. Such series make it convenient to conduct experi­ ments that evaluate reactivity as a function of stereochemistry. Many b io lo g ic a lly important compounds, ex p ecially nucleo­ sides^ ^ and antibiotics ,^1 ^ contain unusual sugars and there has (1) E. Walton, S. R. Jenkins, R. F. Nutt, M. Zimmerman, F. H Helly, J. Amer. Chem. Soe., ;88, 4.524. (1966). (2) E. J. Reist, D, E, Gueffroy, and L. Goodman, ibid., 86, 5658 (1964). ------ (3) A. P. Martinea,
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