Catalytic Formal Carbyne Transformation of Phosphorus Ylides

The selective functionalization of unreactive C–H bonds over reactive polar functionalities paves the way for the efficient synthesis of complex molecular frameworks. Here, we report a consecutive C–H alkylation and Wittig-type reaction of phosphorus ylides, enabling the conversion of inert C–H and C=P bonds into C–C and C=C bonds, respectively. Under blue-light irradiation and with the aid of an appropriate photoredox catalyst, a mixture encompassing phosphorus ylides, electron-rich olefins, and unsaturated carbonyl compounds adeptly undergoes a previously elusive three-component cycloaddition. This transformation allows for the rapid construction of the synthetically versatile functionalized six-membered carbocycles from readily available substrates.