Photoredox Nickel‐Catalysed Stille Cross‐Coupling Reactions

Abstract The Stille cross‐coupling reaction is one of the most common strategies for the construction of C−C bonds. Despite notable strides in the advancement of the Stille reaction, persistent challenges persist in hindering its greener evolution. These challenges encompass multiple facets, such as the high cost of precious metals and ligands, the demand for various additives, and the slow reaction rate. In comparison to the dominant palladium‐catalysed Stille reactions, cost‐effective nickel‐catalysed systems lag behind, and enantioconvergent Stille reactions of racemic stannanes remain undeveloped. Herein, we present a pioneering instance of nickel‐catalysed enantioconvergent Stille cross‐coupling reactions of racemic stannane reagents, resulting in the formation of C−C bonds in good to high yields with excellent stereoselectivity. This strategy provides a practical, scalable, and operationally straightforward method for the synthesis of C( sp 3 )−C( sp 3 ), C( sp 3 )−C( sp 2 ), and C( sp 3 )−C( sp ) bonds under exceptionally mild conditions (without additives and bases, ambient temperature). The innovative use of synergistic photoredox/nickel catalysis enables a novel single‐electron transmetalation process of stannane reagents, providing a new research paradigm of Stille reactions.