Unequivocal SRN1 route of vinyl halides with a multitute of competing pathways: reactivity and structure of the vinyl radical intermediate

Unambiguous examples of the vinylic SRN1 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 SRN1 route are documented. The geometry of the Vy• and kinetic parameters for H-abstraction and coupling with Y- are reported.