ortho-Cyanomethylation of aryl fluoroalkyl sulfoxides via a sulfonium–Claisen rearrangement

Abstract

We hereby report the ortho-cyanomethylation of aryl fluoroalkyl sulfoxides with acetonitrile through a sulfonium–Claisen-type rearrangement. This reaction enables the incorporation of two valuable functional groups, such as the cyanomethyl group and the fluoroalkylthio group, into arenes. Remarkably, fluoroalkylthio groups, such as SCFH₂ and SCF₂H, bearing active hydrogen, are well tolerated by the reaction. The success of the reaction relies on the use of an excess amount of acetonitrile and the electronegative effect of fluoroalkyl substituents, both of which promote the electrophilic assembly of sulfoxides with acetonitrile. Consequently, the sulfonium–Claisen rearrangement reaction tolerates a wide variety of fluoroalkyl sulfoxides bearing functional groups including halides, nitriles, ketones, sulfones, and amides, which are appealing for subsequent elaboration and exploration.