d-Alpha, Alpha-Galaoctose and Some of its Derivatives<sup>1</sup>

Maclay, W. D.; Hann, Raymond M.; Hudson, C. S.

doi:10.1021/ja01272a016

Cited by 16 publications

(9 citation statements)

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“…The observed rotation reduced to the basis of the dialdehyde corresponds to [a)7)l=-125.5°. This value is approximately equal in magnitude but is of opposite sign to that found by Maclay and Hudson [7] for the product from a-methyl d-Iyxopyranoside. The residual periodic acid was determined by titration with sodium arsenite.…”

Section: Preparation Methods (A) Preparation Of A·methyl D·lyxopyranocontrasting

confidence: 72%

“…The new compounds are listed in table 1 The structure of our new .a-methyl d-Iyxoside was determined by the application of the periodic oxidation method of Jackson and Hudson [6]. As shown by Maclay and Hudson [7], a-methyl d-Iyxopyranoside is oxidized by periodic acid according to the following equation: …”

Section: Structural and Configurational Relation-ships For The Pentosmentioning

confidence: 99%

See 1 more Smart Citation

Alpha and beta methyl lyxosides, mannosides, gulosides, and heptosides of like configuration

Isbell¹,

Frush²

1940

J. RES. NATL. BUR. STAN.

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Eleven new su~ar der ivatives and numerous optical rotation and hydrolysis measurements are r eported. A comparison of the alpha and beta methyl glucosides, mannosides, galactosides, and gulosides shows that the configurations of all of the asymmetric carbons in the pyranose ring affect the rate of hydrolysis, and that there is no fixed relationship between the configuration of the glycosidic carbon and the relative rates for the hydrolysis of the alpha and beta modifications. The configur ation of carbon 3 appears to influence markedly the relative rates for the hydrolysis of the alpha and beta modifications. Aldo-pyranosides having trans configurations for carbons 1 and 3 are hydrolyzed more slowly than the corr esponding modifications having cis configurations for carbons 1 and 3. This unexpect edly large influence of carbon 3, and the close resemblance of each pent ose t o the corresponding h exose which has t he trans configuration for carbons 3 and 5 are discussed in r elation to t he spacial arrangement of the whole molecule. The similarity of the methyl gulosides and a-glucoheptosides on the one hand, and t he methyl Iyxosides, mannosides, and a-galaheptosides on the other hand, furnishes a substantial basis for the allocation of Iyxose to the mannose series. CONTENTS

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Section: Preparation Methods (A) Preparation Of A·methyl D·lyxopyranocontrasting

confidence: 72%

Section: Structural and Configurational Relation-ships For The Pentosmentioning

confidence: 99%

Alpha and beta methyl lyxosides, mannosides, gulosides, and heptosides of like configuration

Isbell¹,

Frush²

1940

J. RES. NATL. BUR. STAN.

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“…(b) Catalytic osmylation of the benzylated derivative (7) produced a mixture (92%) containing 8-0-benzyl-1,2 : 3,4-di-Oisoprop y lidene-p-L-threO-D-gulOct o-octopyranose (1 6) [ a, 5.47 (d, J , , , 5 Hz, 1-H)] and the a-D-threo-D-gakzcto isomer (17) [S, 5.54 (d, J,., 5 Hz, 1-H)] in the ratio ca. 3: 1, following purification on silica gel with ethyl acetate.…”

Section: Osmylution Experimentsmentioning

confidence: 99%

Higher-carbon sugars. Part 1. The synthesis of some octose sugars via the osmylation of unsaturated precursors

Brimacombe¹,

HANNA²,

Kabir³

et al. 1986

J. Chem. Soc., Perkin Trans. 1

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The stereochemical outcome of the osmium tetraoxide oxidation of a number of unsaturated carbohydrate derivatives, including (€) -and (Z) -6,7-dideoxy-l,2 : 3,4-di-~-isopropylidene-a-o-ga/acto-oct-6-enopyranose (6) and (9), methyl (Z) -6,7 -dideoxy-1,2 : 3,4-di -0-isopropylidene-a-D-galacto-oct -6-enopyranuronate ( 8 ) , and 7,8-dideoxy-1,2 : 3,4-di-0-isopropylidene-a-D-glycero-~-ga/acto-oct-7 -enopyranose (1 0), has been examined. Such oxidations resulted in the preparation of the synthetically usef u I octose derivatives 1,2 : 3,4-d i -0 -isopropy l idene-x -D -erythro -D -ga/acto -octopyranose (1 8) and 1,2: 3,4: 6,7-tr~-~-~sopropyl~dene-~-~-erythro-~-ga/acto-octopyranose (31 ), as well as syntheses of Lthreo-D -ga/acto-octitol (1 4), D-erythro -D-ga/acto-octitol (21 ), L-erythro-o-galacto-octitoi (29), and D -threo -D-ga/aCtO-OCtitOI (35).The synthesis of sugars with carbon chains composed of more than six carbon atoms, the so-called higher-carbon sugars,' poses an interesting challenge.'-4 Such syntheses require the formation of carbon-carbon bonds and control of the stereochemistry at each newly created stereocentre. The concept of asymmetric synthesis was first realised with the Kiliani-Fischer cyanohydrin reaction, which was used to extend the aldose chain by one carbon atom from the reducing end.2*3 This procedure has been applied to most h e x o s e~,~.~ but, because of the asymmetric nature of the cyanohydrin synthesis, only a limited number of heptoses are available as substrates. In certain cases, syntheses were extended to give octose, nonose, and decose sugars, but the structures of many of these highercarbon sugars remain unproved.' In recent times, the cyanohydrin procedure has been augmented by other methods; ' theseO+ permit extension of the sugar chain by two or more carbon atoms in a single step, but seldom in a wholly predictable way, so that in spite of the long standing interest in higher-carbon sugars, only a handful of them containing eight or more carbon atoms are known.2 A resurgence of interest in the synthesis of higher-carbon sugars has followed the discovery of important antibiotics containing such higher-carbon sugars as the amino-octodioses (1) (from apramycin and oxyapramycin ') and the undecose hikosamine 8*9 (2) (from hikizimycin 9). Our interest in the synthesis of these and other higher-carbon sugars of biological interest prompted an examination of the oxidation of various unsaturated sugar derivatives with osmium tetraoxide. In choosing this approach we were influenced by the knowledge that the osmylation of allylic alcohols and ethers proceeds with moderate to marked stereoselectivity, which can be predicted on an empirical basis. l o Initially our efforts were directed towards the synthesis of octose sugars by extending the chain of the hexodialdose" (3) by two carbon atoms, as outlined in the Scheme. Unlike traditional methods, the carbon chain of the original hexose, in this instance D-galactose, is undergoing extension from the non-reducing end. This particular system...

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“…<f-a,a-Galaoctonic amide has been formed by the action of liquid ammonia on the lactone of d-a.a-galaoctonic acid (87). 2,4,6,-Trimethyl-Sgluconolactone and 3,4,fi-trimethyl-5-altronolactone have been converted into the corresponding amides by solution in liquid ammonia at -33°C.…”

Section: Ohmentioning

confidence: 99%

Liquid ammonia research in 1938—A review

Watt¹,

Cappel²

1939

J. Chem. Educ.

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d-Alpha, Alpha-Galaoctose and Some of its Derivatives¹

Cited by 16 publications

References 0 publications

Alpha and beta methyl lyxosides, mannosides, gulosides, and heptosides of like configuration

Alpha and beta methyl lyxosides, mannosides, gulosides, and heptosides of like configuration

Higher-carbon sugars. Part 1. The synthesis of some octose sugars via the osmylation of unsaturated precursors

Liquid ammonia research in 1938—A review

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d-Alpha, Alpha-Galaoctose and Some of its Derivatives1

Cited by 16 publications

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Alpha and beta methyl lyxosides, mannosides, gulosides, and heptosides of like configuration

Alpha and beta methyl lyxosides, mannosides, gulosides, and heptosides of like configuration

Higher-carbon sugars. Part 1. The synthesis of some octose sugars via the osmylation of unsaturated precursors

Liquid ammonia research in 1938—A review

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d-Alpha, Alpha-Galaoctose and Some of its Derivatives¹