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Syntheses of Amino Sugars

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Syntheses of Amino Sugars SYNTHESES OF AMINO SUGARS AND AMINO ALDITOLS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By ROBERT KRICK ARIvISTRONG, B. S., M. Sc. THE OHIO STATE UMVERSITY 1958 Approved by Adviser Department of Chemistry ACKNOWLEDGMENT The author vdshes to express his appreciation to Professor M. L. ITolfrom for his advice and interest in this work. Dr. F. Shafizadeh has given freely of his time and advice in technical matters, for which the author is grateful. Acknowledgment is extended to the Ohio State University and the Department of Health, Education and Welfare, Public Health Service, National Institutes of Health for assistantships provided by them. ii TABLE OF CONTFi'îTS INTRODUCTION ....................................... 1 STATEvlE'IT OF THE PROBLEM............................. S HISTORICAL....................................... 6 Syntheses of Andzio Alditols .............. 6 Reduction of nitrogeneous derivatives of sugars .................... 6 Opening of epoxide rings Tïith nitrogen b a s e s ...................... 9 Displacement by nitrogen b a s e s ..................................... 10 Syntheses of Amino Sugars ...................... 11 Cyanohydrin s y n t h e s i s .................... 11 Opening of epoxide rings •viith nitrogen b a s e s ........................ 12 Displacement by nitrogen bases . .......................... 16 Degradation of amino sugars................................ 18 Epimerization of amino sugars................................ 19 The Amadori reaction........................ 21 Reduction of nitrogenous derivatives of sugars ....................... 22 Condensation with nitrogen bases .............................. 2k DISCUSSION OF RESULTS .............................. 2$ Syntheses of Amino Alditols....................... 25 iii TABLE OF CONTENTS (Contd.) Preparation of D-gulose phenylhydrazone......................... 26 The reduction of D-gulose and D-arabinose phenylhydrazones , ............ 27 Synthesis of derivatives of 1-amino-l-deoxy-D-galactitol, gulitol and arabinitol.................. 27 Attempted synthesis of 1-amino-l-deoxylactitol 28 Synthesis of 1,2-dideoxy- 1 , 2-bis(sali cylideneamino)- D-glucitol.............................. 29 Synthesis of l,2-dideoxy-l,2- bis(salicylideneamino)- D-mannitol ..... ...................... 30 Attempted reduction of D-3tylo hexose and D-erythro pentose phenylosazones........................... 32 Attempted reduction of D-fructose phenylhydrazone......................... 33 Attempted synthesis of 1,3- dideoxy-1,3 bis (salicylideneamino)- D-glucitol............................... 33 Syntheses of Amino S u g a r s ...................... 33 Synthesis of 3-araino-3-deoxy- 1 ,2 ;$,6-dl-O-isopropylidene-a- D-glucofuranose......... 3U Synthesis of derivatives of 3-amino- 3-deoxy-l,2 ;$, 6-di-O-isopropylidene- a-D-glucofuranose T ...................... 3$ Synthesis of a new pentosamine 2~amino-2-deoxy-a-D-(and L)- arabino(?)-pentose ........................ 36 iv TABLE OF CONTENTS (Contd.) Configuration of 2-amino-2- deoxy-a-D-(and L)-arabino(?)- p e n t o s e ................................. 37 Color tests and properties of 2-amino-2-deoxy-a-D-(and L)- arabino(?)-pentose ........................ 38 Derivatives of 2-amino-2-deoxy-a- D-(and L)-arabino(? ) -pentose............... ii3 Synthesis of $-amin0-$-deoxy-1,2-0- isopropylidene-a-D-xylofuranose ~ £-toluenesulfonate ........................ h3 Synthesis of 3 ,S-diamino-3 ,^-dideoxy- 1,2-0-isopropylidene-a-D-xylo(?)- pentÔfuranose di-£-toluenesulfonate....... hh Synthesis of methyl 6-amino-6-deoxy- 3 ,U-0-isopropylidene-a-D-galacto- pyranoside g-toluenesulfonate......... Ui Synthesis of methyl 2-deoxy-3,^-0- isopropylidene-2-sali cylideneamino- D-xylo(?)-pent0 furanos id e ................. h$ EXPEREÆNTAL....................................... U6 Syntheses of Amino Alditols.................... ii6 Preparation of D-gulose phenylhydrazone.......................... U6 Synthesis of 1-deoxy-l- salicylideneamino-D-gulitol............... k? Synthesis of 1-amino-l-deoxy- D-galactitol hydrobromide ................. U8 Synthesis of l-deoxy-l-(2,U- dinitroanilino) -D-galactitol............... Ii8 Synthesis of 1-deoxy-l- salicylideneamino-D-arabinitol............. U8 TABLE OF CGNTEîITS (Contd.) Page Synthesis of l-amino-l-deoxy- D-arabinitol hydrobromide................ Synthesis of l-deoxy-l-(2,U- dinitroanillno ) -3-arabinitol............... 1|9 Attenpted synthesis of 1- amino-l-deoxylactitol .................... $0 Synthesis of l,2-dideoxy-l,2-bis- (salicylidenearaino)-D-glucitol ............. $1 Synthesis of l,2-dideoxy-l,2-bis- ( salicylideneamino)-D-mannitol............. $2 Attempted reduction of D-xylo- hexose phenylosazone ...................... $3 Attempted reduction of D-erythro- pentose phenylosazone .................... 53 Attempted reduction of D- fructose phenylhydrazone ................... 53 Attempted synthesis of 1,3- dideo:qy-l,3-bis (salicylideneamino ) - D-glucitol............................... 5U Syntheses of Amino S u g a r s ..................... 55 Synthesis of 3-amino-3-deoxy-l,2*5,6- dl-O-isopropylidene-c-D-gluco fi ranose .... 55 Synthesis of 3-deoxy-1,2%5j6-di-O- isopropylidene-3 -salicylideneamino- a-D-glucofuranose ........................ 55 Synthesis of 3-amino-3-deoxy-l,2:5,6- di-O-i sopropyliden e-c-D-gluco furanos e p i c r a t e ................................. 56 Synthesis of 3-amino-N-benzyloxycarbonyl 3-deoxy-1,2*5 » 6-di-O-Tsopropylidene- a-D-glucofuranose T .................. 56 vi TABLE OF CONTENTS (Contd.) Preparation of metJiyl 3>U-0- isopropylidene-p-Ir-arabinopyranoside....... ^7 Preparation of methyl 3^U-0-isopropylidene- 2-0-g-tolylsulfonyl-p-L-arabinopyranoside . $7 Synthesis of methyl 2-deoxy-3,U-0- isopropylidene-2-sali cylideneamino- p-L^rabino( ? )-pentopyranoside ...... 58 Synthesis of methyl 2-amino-2- deoxy-g-L-arabino(?)-pentopyranoside hydrochloride........................ 59 Ifydrolysis of methyl 2-amino-2- deoxy-p-L-arabino(?)-pentopyranoside hydrochloride and methyl p-L- arabinopyranoside.................... 60 Synthesis of 2-amino-2-deoxy-a-L- arabino (?) -pentose hydrochloride....... 60 Synthesis of 2-acetamido-2-deoxy- L-arabino(?)-pentose .................... 61 Synthesis of 2-amino-N^-benzyloxycarbonyl 2-deoxy-L-arabino( ? ) -pentose............... 62 Attempted synthesis of 2-deoxy-2- salicylideneamino-L-arabino ( ? ) - pentose ............................... 62 Attempted synthesis of 2-deoxy-2- ( 2 -hy droxynaphthylideneamino ) -L- arabino(?)-p entose........................ 62 Dische color test for amino suga r s ............................. 63 Synthesis of methyl 2-deoxy-3,U-0- is opropylidene-2-sali cylideneamino- p -P-4irabino( ? ) -pentopyranoside............. 63 Synthesis of methyl 2-amino-2-deoxy- p-D-arabino(?)-pentopyranoside hydrochloride ............................ 6U Tii TABLE OF CONTENTS (Contd.) Synthesis of methyl 2-benzylideneamino- 2~deoxy-0-D-a,rabino(? )-pentopyranoside .... 6^ Synthesis of 2-amino-2-deoxy-a-D- arabino(?)-pentose hydrochloride ........... 65 Synthesis of 5-amino-5-deoxy-l,2-0- isopropylidene-a-D-xylofuranose ~ £-toluenesulfonate ........................ 66 Preparation of 1,2-0-isopropylidene- 3 j 5-di-0-p-tolylsul7onyl-g-D-x5do- fnTcinose ................... 6y Synthesis of 3 ,5-diamino-3,5-dideoxy- l,2-0-isopropylidene-q-D-xylo(? )- pentÔfuranose cü-g-toluenesùlfonate....... 67 Synthesis of methyl 6-amino-6-deoxy- 3 ,li-0-isopropylidene-a-D-galacto- pyranoside £-toluenesulfonate............ 68 Synthesis of mettyl 2-deoxy-3,5-0- isopropylidene-2-sali cyliden earn ino-D- xylo(?;-pentofuranoside .................. 69 SUMMARY ..................................... 70 CHRONOLOGICAL BIBLIOŒAPHY.......................... 73 AUTOEIOBRAPHÏ ..................................... 81 viii LIST OF FIGUÎÎES Page Figure No. 1. Mutarotation of the 2~Amino~2~deoxy- a-L-pentose îiydrochloride in Aqueous Solution................................. UO 2. Intensity of the Color Developed in the Dische T e s t ........................ ii.2 is INTRODUCTION Carbohydrates, together iiith proteins and fats, constitute the major organic components of plants and animals where they serve as structural and reserve materials and maintain the activity of the living cells. The importance of carbohydrates as products of photosynthesis in plants, and as sources of energy for animals, has been reflected in the intense studies made on D-glucose, the principal member of this class of compounds. The vital biological functions of D-glucose and the mechanism of its metabolism are known in considerable detail. The roles of other carbohydrates in nature have not been so extensively investigated. Among these are the amino sugars. These constitute a group of biologically significant compounds. D-GLucosamine, 2-amino-2-deoxy-D-glucose, first isolated by Ledderhose (l), represents the most inportant member of this group. (1) G. Ledderhose, Ber., 9, 1200 (1876). Chitin is a polysaccharide composed entirely of N-acetylated D-glucosamine units. It is found in the structural tissues of the lower members of the animal kingdom. The best sources are the shells of crab, shrimp, and lobster. Acid hydrolysis of the important and chemically complex polysaccharide heparin gives D-glucosamine and I>>glucuronic acid. Heparin is a blood anticoagulant and is isolated from the lung, liver, thymus, spleen and blood. Another polysaccharide which on acid hydrolysis gives
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