Unequivocal S(RN)1 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.
Galli
Carlo
C
Dipartimento di Chimica and Centro CNR Meccanismi di Reazione, Università "La Sapienza", P le A. Moro 5, 00185 Roma, Italy.
Rappoport
Zvi
Z