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Stereoselectivity in the Lewis acid mediated reduction of ketofuranoses
Erwin R van Rijssel1, Pieter van Delft1, Daan V van Marle1
1Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Abstract:
The Lewis acid mediated reduction of ribose-, arabinose-, xylose-, and lyxose-derived methyl and phenyl ketofuranoses with triethylsilane as nucleophile was found to proceed with good to excellent stereoselectivity to provide the 1,2-cis addition products. The methyl ketoses reacted in a more stereoselective manner than their phenyl counterparts. The stereochemical outcome of the reactions parallels the relative stability of the oxocarbenium ion conformers involved, as assessed by calculating the free energy surface maps of their complete conformational space. The Lewis acid mediated reduction allows for a direct synthesis of C-glycosides with predictable stereochemistry.
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