α-Perfluoroalkyl-β-alkynylation of alkenes via radical alkynyl migration

Transition metal-free radical α-perfluoroalkylation with concomitant β-alkynylation of unactivated alkenes is presented. These cascades proceed electron-catalysis and comprise a radical 1,4- or 1,5-alkynyl migration from tertiary propargylic alcoholates to secondary or tertiary C-radicals as the key step. Alkynyl migration leads to a ketyl radical anion that sustains the chain as a single electron transfer reducing reagent.