Diastereoselective C−C Bond Formation at C-5 of Vinyl Sulfone-Modified Hex-5-enofuranosyl Carbohydrates: Diversity-Oriented Synthesis of Branched-Chain Sugars and Beyond

This is the first report on the diastereoselective addition of carbon nucleophiles to vinyl sulfone-modified
hex-5-enofuranosides. The stereoelectronic properties of the substituents at the C-3 position and their
interactions with the incoming carbon nucleophiles control the diastereoselectivity of addition at the C-5
position, favoring the formation of l-ido derivatives as major products in most of the cases studied. This
new concept of stereocontrolled carbon−carbon bond formation in vinyl sulfone-modified carbohydrates
is general in nature. The novel chirons generated by this diversity-oriented synthetic method have been
implemented in the preparation of a wide range of hexofuranosyl C-5 branched-chain sugars, bicyclic
derivatives, chirally pure enals, and densely functionalized carbocycles.