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. Synthese nach Bedarf: Eine diastereodivergente, enantioselektive borylierende Kupplung zwischen Styrolen und Aldiminen unter Kupfer(I)‐Katalyse wird beschrieben. Durch die Kombination von katalysatorkontrollierter Stereodivergenz und von der C‐B‐Bindung abhängiger Konstitutionsdivergenz kann ein breites Spektrum von Aminderivaten mit präziser Chiralitätskontrolle synthetisiert werden.