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Full Paper
Alkoxyallene-Based De Novo Synthesis of Rare Deoxy Sugars: New Routes to L-Cymarose, L-Sarmentose, L-Diginose and L-Oleandrose
Article first published online: 16 JUN 2009
DOI: 10.1002/ejoc.200900450
Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Brasholz, M. and Reißig, H.-U. (2009), Alkoxyallene-Based De Novo Synthesis of Rare Deoxy Sugars: New Routes to L-Cymarose, L-Sarmentose, L-Diginose and L-Oleandrose. European Journal of Organic Chemistry, 2009: 3595–3604. doi: 10.1002/ejoc.200900450
Publication History
- Issue published online: 6 JUL 2009
- Article first published online: 16 JUN 2009
- Manuscript Received: 24 APR 2009
Funded by
- Fonds der Chemischen Industrie
- Deutsche Forschungsgemeinschaft (DFG)
- Bayer Schering Pharma AG
Keywords:
- Total synthesis;
- Carbohydrates;
- Deoxy sugars;
- Glycosylation;
- Gold catalysis;
- Allenes;
- Oxygen heterocycles;
- Furans
Graphical Abstract
Stereodivergent toward four rare 2,6-dideoxyhexoses! Starting from lithiated methoxyallene and (S)-lactaldehyde derivatives,a C3 + C3 approach allows the efficient synthesis of L-cymarose, L-sarmentose, L-diginose and L-oleandrose.
Abstract
Starting from lithiated methoxyallene and lactaldehyde derivatives, the four rare 2,6-dideoxy-hexoses L-cymarose, L-sarmentose, L-diginose and L-oleandrose were synthesized in a stereodivergent fashion. Key steps towards these four target monosaccharides were the oxidative ring openings of allene-derived 2,5-dihydrofurans, diastereoselective carbonyl reductions as well as face-selective hydrogenation protocols. First glycosylation reactions employing thiophenyl glycosyl donors of L-cymarose and L-diginose were performed in high yields and with fair to excellent stereocontrol. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)