Unraveling the Potential of Vinyl Ether as an Ethylene Surrogate in Heteroarene C─H Functionalization via the Spin‐Center Shift

Abstract Despite the simplicity and abundance of ethylene, its practical application presents significant hurdles due to its nature as a highly flammable gas. Herein, a strategic use of easily handled vinyl ether is reported as a latent ethylene surrogate achieved via a spin‐center shift (SCS) pathway, enabling the successful three‐component reaction that bridges heteroarenes and various coupling partners, including sulfinates, thiols, and phosphine oxides. Through a photoredox catalytic process, α‐oxy radicals are generated by combining various radicals with phenyl vinyl ether, which are subsequently added to N‐heteroarenes. Subsequently, the radical‐mediated SCS pathway serves as the driving force for C─O bond cleavage, effectively engaging the phenoxy group as a leaving group. In addition, by broadening the utility of the method, a valuable synthon is provided for efficient C─H vinylation of N‐heteroarenes following sulfonyl group elimination. This approach not only enriches the toolbox of synthetic methodology but also provides a more streamlined alternative, circumventing the challenges associated with direct ethylene gas usage. The versatility of the method, particularly evident in late‐stage functionalizations of medicinally relevant molecules and peptides, underscores its capability to produce invaluable three‐component compounds and vinylated N‐heteroarene derivatives.