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Deoxy and Branched-Chain Sugars This dissertation has been microfilmed exactly as received. M ic 61-912 HANESSIAN, Stephen. DEOXY AND BRANCHED- CHAIN SUGARS. The Ohio State University, Ph.D., 1960 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan DEOXI AND BRANCHED-CHAIN SUGARS DISSERTATION Presented In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State UniTers ity By STEPHEN HANESSIAN, B. Sc. The Ohio State University I960 Approved by Adviser Department of Chemls try ACKKOWLEDOMEIT I would like to dedlaato this dissertation to ay parents. My particular thanks srs to Profsssor M. L. Velfrom for his latorost and advice throughout this lnvestiga- tlon# Ths toehalesl guldsnes given by Ora, F. Shaflsadoh and A. Thompson on many occasions, and ths stimulating dlsousslons with mombars of ths rssoareh group is ac­ knowledged* My thanks arc extended to Ora. H. El-Khaden and M. A. El- Taraboulal of the University of Alexandria, Alexandria, Egypt, for arousing my interest la the field of carbohydrate ohemlstry, and for encouraging me to further ay studies* Lastly, I wish to acknowledge the financial assistance given by the Department of Health, Educa­ tion and Velfare, Public Health Service, national Institutes of Health (1957-1959, 1960-present) and also the C. F. Kettering Eeseareh Foundation (1959- 1960). 11 TABLE OF CONTENTS fagft INTRODUCTION .................................... 1 STATEMENT OF THE PROBLEM ...................... 6 HISTORICAL ...................................... 8 Synthesis of Acyclic Dialdose Derivatives .. 8 Oxidative Methods ....................... 8 Reductive Methods ....................... 10 Synthesis of Acyclic Dicarbonyl (Aldulose and Diulose)Derivetives ..................... 16 Hydrolytic Methods ................... 16 Synthetic Methods .......... 19 Oxidative Methods ....................... 21 The Reaction of Carbohydrates with Grignard Reagents ........... 27 Glycosyl Halides ...................... 27 Lactones, nclds and Esters ............. 30 Acyclic Aldose and aldulose Derivatives 32 Anhydro Sugars . ........................ 34- Synthesis of Unsaturated Sugar Derivatives through Grignard Reactions ...... 36 Synthesis of Terminal Deoxy Hexoses ........ 45 Epimerization Methods ................... 45 Reductive Methods ....... 48 Terminal halo derivatives ........ 48 Terminal unsaturated (didehydro) sugars and glycoseens ............... 51 Terminal anhydro sugars ............ 52 Terminal sulfonyloxy and mercapto derivatives ............... 53 ill Table of Contents (contd.) Page Oxidative Methods ............................ 55 Enzymic Methods .............................. 56 The Synthesis of Branched-Chein Sugars ........ 62 The £-Hydroxymethyl Sugars .................. 62 The £-hydroxymethy1 tetroses ......... 62 The £ “hydroxymethyl pentoses .......... 65 The £-hydroxymethyl hexoses .......... 66 The £-Formyl Sugars .......................... 67 The £-formyl pentoses .................. 67 Other £-formyl sugars ........... 68 The £-Alkyl and £.-Aryl Sugars ............... 69 Terminal di—,C-substit uted sugars ..... 69 The 3-,0-methyl hexoses ................. 70 DISCUSSION OF hSS'JLTS ............................... 75 The Preparation of Dimeric 1,2—Q- is opropvlidene-5-aldehvdo-D-xvlo- 1 . 4-furano-pentodia Idose .............. 75 The Synthesis of 3-_Q—Benzyl-1,2-_Q- isopropylidene-S-aldehydo-D-xylo- l ^ - f urano-pentodialdose (ill) ................ 77 The Synthesis of Monomeric 1,2-.Q- lsopropvlidene-5-aldehvdo-D-xvlo- 1 14-furano—pentodia Idose (V) .................. 80 The Synthesis of D-xvlo-Pentodlaidose (VI) .... 82 The heaction of 3-_0-Benzyl-1 ,2- 0- isopropylide ne-5-aldehydo-D-xylo- 1 .4-furano-pentod ialdose with Me thylmagneaium iodide - The Synthesis of 3-0-Ben zyl-6-deoxy-lr 2-_Q-i s opropylldene- L-ldof uranose .................................... 84. The Assignment of .jtereochemical Configuration to the Grignard i.esction Product .......................................... 89 iv Table of Contents (contd.) Page Investigation of the Mother Liquors of the Grignard Product .......................... 94 An Explanation for the Apparent Stereospeclficity In the Grignard Reaction ....................................... 95 The Synthesis of 3-.Q-Bensyl-6-deoxy- L-idose (IX) and soae of Its Derivatives .... 103 The Atteapted Preparation of 6-Deoxy- L-idose ........................................ 108 An Interpretation of the Results Concerning the Preparation of 6-Deoxy-L-ldoae................................. 119 The Synthesis of 6-Deoxy-D-glucose Derivatives .................................... 125 The Synthesis of 3-.2~BenByl-6-deoxy- 1 f 2-0-isopropvlldene-D-xvlo-l,4- furano— 5-hexosulose (XXIII ) .............. «... 128 The Carbonyl Reduction of 3-£-Benzyl- 6-deoxy-l, 2-^2-is opr opvlidene-D-xvlo- 1,4-furano-5-hexoaulose with Metal Hydrides ....................................... 132 An Interpretation of the Results of the Metal Hydride Reductions ..................... 135 The Synthesis of 3-.2-B ensyl-1,2-£- isopropylidene-5,5-di-£-methyl-D- xylofuranose (XXIV) ........................... 139 The Synthesis of l,2-£-Isopropylidene-5,5- di-£-methyl-D-xylof uranose (XXV) ............ 140 The Acetolysis of 3,5-Di-£-benzoyl- l,2-£—isopropylldene—5 , 5-di-£-methyl- D-xylofur anose (XXVII) ........................ 141 The Synthesis of 5,5-Di-£-methyl- D-xylose (XXIX) ............................... 144 Soae Crystalline Derivatives of 5, 5-Di-£-jnethyl-D-xylose ..................... 146 v Table of Contents (contd.) L a s * EXPERIMENTAL ...................................... 149 The Synthesis of D»xylo-pentodisIdose and Derivatives ............. 149 The Preparation of Dimeric 1,2 laopropvlidane-5-aldahydo-D-XYlo- 1,4“furano-pentodialdoae .................. 149 The Preparation of 3-fl-Banayl-l,2-_Q- laopropylidene-D-glucofuranose (I) ....... 151 The Synthesis of 3-.S2-Benayl-l,2-.fi­ ls opr opylidene-5,6-bis-,2- (p-nitro- benzoyl)-D-glucofuranose (Tl) ............. 152 The Synthesis of 3-fi-Benzy 1-1,2-.fi- isopropylidene-5-aldehydo-D-xylo- 1.4-furano-pentodlaldoae (III) ............ 153 The Synthesis of 3-fi-Benzyl-l, 2-.fi- lsopropylIdene-5-aldehydo-D-zylo- 1.4-furano-pentodla Idose Semlcarba zone (IV) ......................... 156 The Synthesis of 1,2-fi-Isopropylidene- 5-aldehydo-D-xylo-l.4-furano- pent odlaldose (V) ......................... 156 The Synthesis of D-xvlo-pentodlaldose (VI). 158 The Synthesis of 6-Deoxy-L-idose and Deriyatives ................................. 159 The Synthesis of 3-.fi-Benzyl-6-deoxy- 1 12-fi-is opropylldene-L-idof uranose (VII) .. 159 General description of the Grignard apparatus ...................... 159 A. The Grignard Reaction Using Ether as Solvent ................ 160 B. The Grignard Reaction Using Benzene-Ether as Solvent ......... 163 C. The Grignard Reaction Using Tetrahydrofuran as Solvent ........ 164 Normal addition ..................... I64 Inverse addition ................... 165 vi Table of Contents (contd.) Page The Synthesis of 3-.2-Benayl-6- de oxy-1,2-£-1 s opr opyll dene-5-j2- methylaulfonyl-L-idofuranose (VIII) ............ 165 The Stereochemical Configuration of the Product from the Grignard Reaction- The Preparation of 6-Deoxy-lf 2-£- isopropylldene-L-ldofuranoae (IX) ............. 166 The Preparation of 3> 5-Di-,Q-acetyl- 6-deoxy-l, 2-£-isopr opylldene-L- idofuranose (X) ................................. 168 Investigation of the Mother uiquors from the Grignard Reaction ..................... 168 attempted purification ...................... 168 Hydrogenolysia of mother liquors ........... 170 4. Grignard Reaction Using Ether as Solvent ........................ 170 B. Grignard Reaction Using Benzene-Ether as Solvent ................ 171 C. Grignard Reaction Using Tetrahydrofuran as Solvent ............. 171 The Synthesis of 3-0-Benzyl- 6-deoxy-L-idose (XI) ............................ 172 The Synthesis of 3-i)-Benzyl-6-deoxy- L-idose Benzylphenylhydrazone (XII) ........... 173 The Synthesis of 3-<2-Benzyl-6- deoxy-R-idose Phenylosazone (XIII) ............ 174 The Synthesis of Tri-.Q-acetyl-3-.2- benzyl-6-deoxy-L-idose (XIV ) ................... 175 4. Sodium Acetate Method ................... 175 B. 4cetlo Anhydrlde-Pyridine Method .................................... 17b The Synthesis of 1,2,4-Tri-O-acety1- 6-deoxy-L-idose (XV) ............................ 177 vii Table of Contents (contd.) Page The Synthesis of 1,2,3,4**Tetra-.2“ acetyl-6-deoxy-L-idose (XVI) .............. 177 The Syntheala of 3-\Q“Bensyl- 6-deoxy-L-iditol (XVII) ................... 178 The Syntheala of Tetra-£-acetyl- 3-£-ben*yl-L-iditol (XVIII) ............... 179 The Attempted Preparation of 6-Deoxy-L-ldoae ............................. 179 A. Resin Hydrolysis of 6-Deoxy- 1,2-£-lsopropylldene-L- idofuranoae (IX) ................... 179 Column Chromatography .......... 180 Paper Chromatography ........... 181 B. Acid Hydrolysis of 6-Deoxy- 1»2-^-iaopropylidene-L- ldofuranose (IX) ................... 184 C. Hydrogenolysis of 3-,fi-B«n*yl- 6-deoxy-L-idose (XI)................ I84 Behavior of the hydrogenolysIs product in acid solution ....... 186 The Synthesis of 6-Deoxy-D- glucose Derivatives ........................... 187 The Preparation of 3-5-Benayl-l,2-.Q- lsopropylidene-6— p-tolylsulfonyl- D-glucofuranose (XlT) ...................... 187 The Synthesis of 3—D —Benayl—6— deoxy—1,2—.Q—is opropylId ene—D- glucof uranose (XX) ......................... 188 The Preparation of 6-Deoxy-l,2-0- isopropylidene-D-glucofuranose
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