Asymmetric Catalytic Halofunctionalization of α,β-Unsaturated Carbonyl Compounds.

Halofunctionalization methods enable the vicinal difunctionalization of alkenes with heteroatom nucleophiles and halogen moieties. As a fundamental transformation in organic synthesis, the catalytic asymmetric variants have only recently been reported. In sharp contrast to the asymmetric halocyclization of simple alkenes which involves a nucleophile-assisted alkene activation process, the asymmetric halofunctionalization of enones developed by our laboratory features an electrophile-assisted 1,4-addition pathway. Our work in this area has resulted in the development of several different types of regio-, diastereo-, and enantioselective processes, including inter- and intramolecular haloaminations, haloetherifications, and haloazidations. The scope, updated mechanism, limitations, and future perspective of these reactions are discussed.