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 α-position of the carbonyl group for facile access to trifluoromethyl α-halo- and α-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.