Enantioselective Synthesis of Axially Chiral Allylic Nitriles via Nickel‐Catalyzed Desymmetric Cyanation of Biaryl Diallylic Alcohols

Abstract Axially chiral nitriles are common motifs in organic photoelectric materials, biological compounds, and agrochemicals. Unfortunately, the limited synthetic approaches to axially chiral nitriles have impeded their availability. Herein, we report the first nickel‐catalyzed desymmetric allylic cyanation of biaryl allylic alcohols for the synthesis of axially chiral nitrile structures in high yields with excellent enantioselectivities (up to 90 % yield and >99 % ee ). This process enables the synthesis of a diverse range of axially chiral allylic nitriles bearing β , γ ‐unsaturated alcohol moieties. Leveraging the allylic alcohol and cyano groups as versatile functionalization handles allow for further derivatization of these axially chiral frameworks. Density functional theory (DFT) calculations suggest that both steric and electronic interactions play crucial roles in determining the enantioselectivity of this transformation. Moreover, this mild and facile protocol is also applicable for gram‐scale preparation of the chiral nitriles.