Ecofriendly Borylation of Allylic Acetates via Nickel‐Catalyzed Dual‐Role Base Activation

Allylic boronates are valuable synthons in organic chemistry, making the development of efficient and sustainable preparation methods highly desirable. A nickel‐catalyzed borylation of unactivated allylic acetates using a recyclable N‐donor ligand system in ethyl acetate is reported. The method employs an innovative dual‐role base that simultaneously activates diboron reagents and reduces air‐stable NiBr 2 , eliminating the need for external reductants. The approach shows excellent compatibility across a diverse array of substrates, delivering the desired products with isolated yields up to 97%. Its operational simplicity is evidenced by glovebox‐free conditions and successful multigram‐scale implementation (13 mmol scale, yields up to 95%), underscoring the method's practicality as a ecofriendly alternative to conventional allylic borylation.