Nickel‐Catalyzed Cross‐Electrophile 1,2‐Silyl‐Arylation of 1,3‐Dienes with Chlorosilanes and Aryl Bromides

Abstract Catalytic, three‐component, cross‐electrophile reactions have recently emerged as a promising tool for molecular diversification, but studies have focused mainly on the alkyl‐carbonations of alkenes. Herein, the scope of this method has been extended to conjugated dienes and silicon chemistry through silylative difunctionalization of 1,3‐dienes with chlorosilanes and aryl bromides. The reaction proceeds under mild conditions to afford 1,2‐linear‐silylated products, a selectivity that is different to those obtained from conventional methods via an intermediary of H(C)‐η 3 ‐π‐allylmetal species. Preliminary mechanistic studies reveal that chlorosilane reacts with 1,3‐diene first and then couples with aryl bromide.