This review covers the recent progress in electro-/photo-catalytic alkene-derived radical cation chemistry for organic synthesis, including synthetic strategies, plausible mechanisms and further research outlook.

A new electrochemical intermolecular 1,2-aminosulfonylation of alkenes with sulfinates and amines is achieved by utilizing balanced threecomponent interactions and reactivity differentiation. This strategy can be applicable to a wide range of amines, including primary and secondary amines, thus enabling alkene aminosulfonylation for producing diverse functionalized 2-sulfonylethan-1amines without the need of additive redox catalysts, metal catalysts and chemical oxidants.

A general, ideal atom utilization electrochemical technology to enable alkene alkoxyhalogenation and organohalide dehalogenation in one pot is presented. This technology is highlighted by convergent strategy integrating several reactions, such as alkene alkoxyhalogenation, organohalide dehalogenation, and dehalogenation deuteration. Experimental data suggest that alkenes have the lowest oxidation potential, which lead to anodic conversion of the CC bond to the radical cation intermediates, and cathodic transformations of organohalides, including alkyl and aryl halides, as the nucleophilic halogen sources.

Ac obalt-promoted electrochemical 1,2-diarylation of alkenes with electron-rich aromatic hydrocarbons via direct dual CÀHf unctionalizations is described, whiche mploys ar adical relay strategy to produce polyaryl-functionalized alkanes.S imply by using graphite rod cathode instead of platinum plate cathode,c hemoselectivity of this radical relay strategy is shifted to the dehydrogenative [2+ +2+ +2] cycloaddition via 1,2-diarylation, annulation, and dehydrogenation cascades leading to complex 11,12-dihydroindolo[2,3-a]carbazoles.M echanistical studies indicate that ak ey step for the radical relayp rocesses is transformations of the aromatic hydrocarbons to the aryl sp 2-hybridized carbon-centered radicals via deprotonation of the corresponding aryl radical cation intermediates with bases.