Asymmetric Synthesis of Axially Chiral Olefins and Heterobiaryls via Rhodium-Catalyzed C–C Activation and [4 + 2] Annulation

Axially chiral biaryls are privileged scaffolds in chiral ligands, catalysts, and functional molecules. Reported herein is rhodium-catalyzed atroposelective [4 + 2] annulation of benzocyclobutenols with alkynes. The coupling system is chemodivergent under silver additive control as a result of controlled dehydration in post-annulation reactions, affording axially chiral heterobiaryls or olefins in excellent regio- and enantioselectivity.