Unequivocal SRN1 Route of Vinyl Halides with a Multitude of Competing Pathways: Reactivity and Structure of the Vinyl Radical Intermediate

Unambiguous examples of the vinylic S(RN)1 reaction initiated by a single-electron transfer from an electron-donor anion (Y(-)) to a suitable VyX substrate, and proceeding through a vinyl radical (Vy(*)()) intermediate, are described. Competition by alternative substitution routes is extensive, but through a systematic modification of the structure of the substrate, unequivocal examples of the vinylic S(RN)1 route are documented. The geometry of the Vy(*)() and kinetic parameters for H-abstraction and coupling with Y(-) are reported.