Rhodium(III)-Catalyzed Three-Component Oxyamidation of Alkynes with CO ₂ Retention from Dioxazolones

Alkyne oxyamidation represents a powerful difunctionalization system toward rapid assembly of tetrasubstituted, electron-rich alkenes. We herein report a Rh(III)-catalyzed three-component oxyamidation protocol utilizing amine, dioxazolone, and indolyl alkyne as substrates. This transformation enables unprecedented utilization of carbon dioxide moiety from dioxazolones─a process that circumvents the stoichiometric CO 2 waste typically associated with dioxazolone-mediated nitrene transfer reaction. Operating under mild conditions, the reaction is characterized by 100% atom-economy, high regioregularity, and exclusive Z -selectivity, which allows efficient and sustainable access to densely functionalized tetrasubstituted alkene scaffolds with broad functional group compatibility.