title: Stereoselectivity in the Lewis acid mediated reduction of ketofuranoses.
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.
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Erwin R
authors.initials: ER
authors.lastname: van Rijssel
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Pieter
authors.initials: P
authors.lastname: van Delft
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Daan V
authors.initials: DV
authors.lastname: van Marle
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Stefan M
authors.initials: SM
authors.lastname: Bijvoets
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Gerrit
authors.initials: G
authors.lastname: Lodder
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Herman S
authors.initials: HS
authors.lastname: Overkleeft
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Gijsbert A
authors.initials: GA
authors.lastname: van der Marel
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Dmitri V
authors.initials: DV
authors.lastname: Filippov
authors.affiliation: Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
authors.forename: Jeroen D C
authors.initials: JD
authors.lastname: Codée