Organoboron Initiated Rh-Catalyzed Asymmetric Cascade Reactions: A Subtle Switch in Regioselectivity Leading to Chiral 3‑Benzazepine Derivatives

An addition-carbocyclization cascade reaction initiated by arylboronic acids and catalyzed by a rhodium/chiral diene complex is described. Starting from N-bridged yne-enoate derivatives, chiral functionalized seven-membered 3-benzazepine heterocycles were obtained with high enantioselectivities, thanks to a rhodium 1,4-shift.