Nickel/photoredox-catalyzed three-component silylacylation of acrylates via chlorine photoelimination

Abstract

The extensive utility of organosilicon compounds across a wide range of disciplines has sparked significant interest in their efficient synthesis. Although catalytic 1,2-silyldifunctionalization of alkenes provides a promising method for the assembly of intricate organosilicon frameworks with atom and step economy, its advancement is hindered by the requirement of an external hydrogen atom transfer (HAT) agent in photoredox catalysis. Herein, we disclose an efficient three-component silylacylation of alpha,beta-unsaturated carbonyl compounds, leveraging a synergistic nickel/photoredox catalysis with various hydrosilanes and aroyl chlorides. This method enables the direct conversion of acrylates into valuable building blocks that contain both carbonyl and silicon functionalities through a single, redox-neutral process. Key to this reaction is the precise activation of the Si-H bond, achieved through chlorine radical-induced HAT, enabled by the photoelimination of a Ni-Cl bond. Acyl chlorides serve a dual role, functioning as both acylating agents and chloride donors. Our methodology is distinguished by its mild conditions and extensive substrate adaptability, significantly enhancing the late-stage functionalization of pharmaceuticals.