Use of Electrochemical Methods as an Alternative to Tin Reagents for the Reduction of Vinyl Halides in Inositol Synthons

Abstract

Several vinyl halides previously used in inositol syntheses were subjected to electrochemical reduction. The unreactivity of allylic alcohols or allylic ethers at the applied potentials allowed the selective reduction of vinyl halides to olefins. Electrochemical methods provide for selective reduction of vinyl iodides over vinyl bromides, with better yields than analogous tin methodology. Cinnamyl ethers were reductively cleaved at -3.2 V (vs Ag/AgNO(3)) in the presence of alkyl allyl ethers to provide selective deprotection. The electrochemical reduction of vinyl halides in the presence of a vinyloxirane or vinylaziridine is accompanied by the solvolysis of the strained rings. Yields and conditions are reported and compared to those from standard tin-induced dehalogenation.