Nickel‐Catalyzed Regio‐ and Enantioselective Migratory Hydrocyanation of Internal Alkenes: Expanding the Scope to α,ω‐Diaryl Internal Alkenes

Abstract Metal‐hydride‐catalyzed migratory functionalization of alkenes witnessed extensive development in the past few years. However, the asymmetric version of this reaction has remained largely underdeveloped owing to the difficulty in simultaneous control of both regio‐ and stereoselectivity. In addition, exploring the wider alkene substrate scope to enable more synthetically valuable applications represents another challenge in this field. In this context, a nickel‐catalyzed asymmetric hydrocyanation of internal alkenes involving a chain‐walking process is demonstrated. The reaction exhibits excellent regio‐ and enantioselectivity, proceeds under mild reaction conditions, and delivers benzylic nitriles in high yields. Even α,ω‐diaryl internal alkenes, which are known to be one of the most challenging substrates of this type, could be successfully converted to the desired products with good regio‐ and stereoselectivity by modifying the electronic and steric effects. Theoretical calculations suggest that the η 3 ‐benzyl coordination mode and the aryl substituent (3,5‐(OMe) 2 C 6 H 3 ) on the diphosphite ligand are both key factors in regulating regio‐ and enantioselectivity.