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.