Chain-Elongation of Sugar Aldehydes by Asymmetric Homoaldol Reaction: Introduction of a Functionalized 3-Methyl-Substituted Three-Carbon Unit

Abstract

O-Protected aldehydo-sugars reacted with α-titanated crotyl N,N-diisopropylcarbamate to furnish chain-elongated alk-1-enyl carbamates. These were further functionalized by epoxidation of the double bond and subsequent methanolysis to form methyl 3-C-methyl-3-deoxy-furanosides. Mukaiyama-type addition of benzaldehyde led to tetrasubstituted tetrahydrofurans. All reactions proceeded with high diastereoselectivities and allow for a broad application.

homoaldol reaction - epoxides - (-)-sparteine-mediated metalation - stereoselective synthesis - branched carbohydrates

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Data sets were collected with Nonius KappaCCD diffractometers, in case of Mo-radiation equipped with a rotating anode generator. Programs used: data collection COLLECT, [32] data reduction Denzo-SMN, [33] absorption correction SORTAV [34] and Denzo, [35] structure solution SHELXS-97, [36] structure refinement SHELXL-97, [37] and graphics SCHAKAL. [38] CCDC 621679 & 621680 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: [phone], E-mail: [e-mail]].

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