Trifluoromethylation-Initiated Remote Cross-Coupling of Carbonyl Compounds to Form Carbon-Heteroatom/Carbon Bonds

By involving the reversal of conventional reactivity expectations without external oxidants, we describe a novel and convenient protocol of remote cross-coupling of carbonyl compounds with a series of common and simple nucleophiles. This cross-coupling is triggered by radical trifluoromethylation of alkenes, thereby achieving highly selective remote difunctionalization of alkenes and alpha-position of the carbonyl group for facile access to trifluoromethyl alpha-halo- and alpha-cyanocarbonyl compounds. The reaction exhibits a broad substrate scope with excellent functionality tolerance and many different types of nucleophiles; further synthetic applicability of the obtained compounds proved to be suitable, thus showing great potential for synthetic utility.