1,2,3-Trifunctionalization of α,α-Disubstituted Vinyl Aldehydes Enabled by Radical 1,2-Migration of Formyl

Abstract

As compared to the well-established 1,2-difunctionalizations, the 1,2,3-trifunctionalization of alkenes has been much less developed, due to the formidable challenges in controlling site-, regio- and diastereoselectivity. Enabled by an uncommon radical-mediated 1,2-migration of carbonyls, a highly controllable 1,2,3-trifunctionalization of α,α-disubstituted vinyl aldehydes with benzoyl peroxide (BPO) as an radical initiator is successfully accomplished, providing a number of trifluoromethylated alkynyl aldehydes in moderate to good yields. Given the site-selective cleavage of allylic C-C bonds and concurrent introduction of three synthetically important functional groups, such as a trifluoromethyl motif, a formyl moiety and an alkyne, it will find widespread applications in both synthetic chemistry and pharmaceutical industry.