Light-Driven <i>N</i>-Heterocyclic Carbene Catalysis Using Alkylborates

Abstract

Radical–radical coupling, the selective reaction between two different radical species, has contributed to the methodology for connecting bulky units. Light-driven N-heterocyclic carbene (NHC) organocatalysis is recognized as a state-of-the-art methodology enabling radical–radical coupling. The catalytic process involves forming an acyl azolium intermediate from the NHC catalyst and an acyl donor, followed by single electron reduction of this key intermediate, which is largely dependent on the photoredox catalyst. We designed a radical NHC catalysis in which the direct photoexcitation of a borate to form a high reducing agent facilitated the single electron reduction event. The borate produces an alkyl radical for the single electron transfer process to accomplish the radical–radical coupling. This protocol enables cross-coupling between alkylborates and acyl imidazoles in addition to radical relay-type alkylacylations of alkenes with alkylborates and acyl imidazoles, affording ketones with a broad scope.