Enantioselective Synthesis of Chiral Cyclopentenes by Relay Catalysis from Terminal Alkynes, Enones, and Syngas

A novel relay catalytic strategy for the asymmetric functionalization of terminal alkynes by synergistically integrating Rh-catalyzed hydroformylation with <i>N</i>-heterocyclic carbene (NHC)-catalyzed asymmetric annulation has been developed. This dual-catalysis platform overrides the innate reactivity of alkynes, enabling direct and efficient access to polysubstituted chiral cyclopentenes from simple terminal alkynes, enones, and syngas. The transformation proceeds smoothly under mild conditions, delivering a broad range of chiral cyclopentenes in good yields, with high diastereoselectivities and excellent enantioselectivities (up to 16:1 dr, up to 99% ee).