Cu/Pd dual catalyzed stereoselective construction of vicinal tri- and tetrasubstituted stereocenters connected to chiral α-arylacetonitriles.

Herein, we report an optimized Pd/Cu bimetallic catalyst that facilitates the stereoselective allylic alkylation of secondary and tertiary nitriles under mild conditions. This method affords homoallylic nitriles with adjacent tri- and tetrasubstituted stereocenters. Using both racemic and enantioselective catalysts, the system exhibits high regio- and enantioselectivity (ee up to 91%). Mechanistic studies and DFT calculations highlight the key synergistic roles of Pd and Cu in controlling both reactivity and enantioselectivity.