Synthesis and properties of 2,3-anhydro-D-mannose and 3,4-anhydro-D-altrose

J. Grant Buchanan, David M Clode

Research output: Contribution to journalArticle

Abstract

Treatment of benzyl 3,4,6-tri-O-acetyl-2-O-p-tolylsulphonyl-ß-D-glucopyranoside (5) with sodium methoxide in methanol gave benzyl 2,3-anhydro-ß-D-mannopyranoside (7) (65%) and benzyl 3,4-anhydro-ß-D-altropyranoside (8) (29%). Hydrogenolysis of the glycoside (7) in tetrahydrofuran over palladium-charcoal yielded crystalline 2,3-anhydro-ß-D-mannopyranose (9) which, in aqueous solution, rapidly underwent mutarotation to give an equilibrium mixture containing the a-pyranose (10) (23%), the ß-pyranose (9) (7%), the a-furanose (12) (65%). and the ß-furanose (11) (5%), whose composition was determined by g.l.c., g.l.c.-mass spectrometry, and n.m.r. spectroscopy; the assignment of anomeric configuration to the furanose isomers rests on conformational arguments. A similar mixture was obtained by hydrogenolysis of benzyl 2,3-anhydro-a-D-mannopyranoside (13). Hydrogenolysis of the glycoside (8) in methanol gave an equilibrium mixture of the a- and ß-forms [(14) and (15)] of 3,4-anhydro-D-altropyranose (32.5 and 67.5%, respectively).

Original languageEnglish
Pages (from-to)388-394
Number of pages7
JournalJournal of the Chemical Society, Perkin Transactions 1
Publication statusPublished - 1974

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Hydrogenolysis
Mannose
Methanol
Glycosides
Charcoal
Palladium
Isomers
Mass spectrometry
Spectroscopy
Crystalline materials
Chemical analysis
D-altrose

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title = "Synthesis and properties of 2,3-anhydro-D-mannose and 3,4-anhydro-D-altrose",
abstract = "Treatment of benzyl 3,4,6-tri-O-acetyl-2-O-p-tolylsulphonyl-{\ss}-D-glucopyranoside (5) with sodium methoxide in methanol gave benzyl 2,3-anhydro-{\ss}-D-mannopyranoside (7) (65{\%}) and benzyl 3,4-anhydro-{\ss}-D-altropyranoside (8) (29{\%}). Hydrogenolysis of the glycoside (7) in tetrahydrofuran over palladium-charcoal yielded crystalline 2,3-anhydro-{\ss}-D-mannopyranose (9) which, in aqueous solution, rapidly underwent mutarotation to give an equilibrium mixture containing the a-pyranose (10) (23{\%}), the {\ss}-pyranose (9) (7{\%}), the a-furanose (12) (65{\%}). and the {\ss}-furanose (11) (5{\%}), whose composition was determined by g.l.c., g.l.c.-mass spectrometry, and n.m.r. spectroscopy; the assignment of anomeric configuration to the furanose isomers rests on conformational arguments. A similar mixture was obtained by hydrogenolysis of benzyl 2,3-anhydro-a-D-mannopyranoside (13). Hydrogenolysis of the glycoside (8) in methanol gave an equilibrium mixture of the a- and {\ss}-forms [(14) and (15)] of 3,4-anhydro-D-altropyranose (32.5 and 67.5{\%}, respectively).",
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journal = "Journal of the Chemical Society, Perkin Transactions 1",
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Synthesis and properties of 2,3-anhydro-D-mannose and 3,4-anhydro-D-altrose. / Buchanan, J. Grant; Clode, David M.

In: Journal of the Chemical Society, Perkin Transactions 1, 1974, p. 388-394.

Research output: Contribution to journalArticle

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T1 - Synthesis and properties of 2,3-anhydro-D-mannose and 3,4-anhydro-D-altrose

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AU - Clode, David M

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AB - Treatment of benzyl 3,4,6-tri-O-acetyl-2-O-p-tolylsulphonyl-ß-D-glucopyranoside (5) with sodium methoxide in methanol gave benzyl 2,3-anhydro-ß-D-mannopyranoside (7) (65%) and benzyl 3,4-anhydro-ß-D-altropyranoside (8) (29%). Hydrogenolysis of the glycoside (7) in tetrahydrofuran over palladium-charcoal yielded crystalline 2,3-anhydro-ß-D-mannopyranose (9) which, in aqueous solution, rapidly underwent mutarotation to give an equilibrium mixture containing the a-pyranose (10) (23%), the ß-pyranose (9) (7%), the a-furanose (12) (65%). and the ß-furanose (11) (5%), whose composition was determined by g.l.c., g.l.c.-mass spectrometry, and n.m.r. spectroscopy; the assignment of anomeric configuration to the furanose isomers rests on conformational arguments. A similar mixture was obtained by hydrogenolysis of benzyl 2,3-anhydro-a-D-mannopyranoside (13). Hydrogenolysis of the glycoside (8) in methanol gave an equilibrium mixture of the a- and ß-forms [(14) and (15)] of 3,4-anhydro-D-altropyranose (32.5 and 67.5%, respectively).

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