Enantioselective Nickel‐Catalyzed Migratory Hydrocyanation of Nonconjugated Dienes

Metal‐catalyzed chain‐walking reactions have recently emerged as a powerful strategy to functionalize remote positions in organic molecules. However, a chain‐walking protocol for nonconjugated dienes remains scarcely reported, and developments are currently ongoing. In this Communication, a nickel‐catalyzed asymmetric hydrocyanation of nonconjugated dienes involving a chain‐walking process is demonstrated. The reaction exhibits excellent regio‐ and chemoselectivity, and a wide range of substrates were tolerated, delivering the products in high yields and enantioselectivities. Deuterium‐labeling experiments support the chain‐walking process, which involves an iterative β‐H elimination and reinsertion processes. Gram‐scale synthesis, regioconvergent experiments, and downstream transformations gave further insights into the high potential of this transformation.