Highly Stereoselective Preparation of Chiral α-Substituted Sulfides from α-Chloro Sulfides via 1,2-Asymmetric Induction

Abstract

A C-S stereogenic center is created with efficient stereo-controlby 1,2-asymmetric induction due to a vicinal C-O stereogeniccenter. Propargylic, allylic, and alkyl sulfides are readily preparedin good yield and stereoselectivity from α-chloro sulfides. Theallylic sulfide have been converted to the corresponding sulfoxide/sulfilimine/sulfurylide and subjected to [2,3]-sigmatropic rearrangement.The efficient 1,3-chirality transfer observed in this reaction eventuallyresults in a net 1,4-chirality transfer.