Copper(I)‐Catalyzed Enantio‐ and Diastereodivergent Borylative Coupling of Styrenes and Imines

We report copper(I)‐catalyzed enantio‐ and diastereodivergent borylative coupling of styrenes and imines to produce enantiomerically‐enriched α,β‐dibranched γ‐boryl amine derivatives. Each of the four possible stereoisomers of the products, derived from the two contiguous stereocenters, was selectively accessible by choosing a proper chiral ligand for the copper catalyst. This method, which combines catalyst‐controlled stereodivergency and constitutional divergency derived from the lynchpin motif (i.e., the C−B bond), offers a strategy for addressing the construction of molecular structural diversity concomitant with precise chirality control. Molecular synthesis on demand: Diastereodivergent, enantioselective borylative coupling between styrenes and aldimines using copper(I) catalysis is reported. By combining catalyst‐controlled stereodivergency and C−B bond‐derived constitutional divergency, a wide range of amine derivatives can be synthesized with precise chirality control.