Asymmetric Paired Electrocatalysis: Enantioselective Olefin–Sulfonylimine Coupling

Abstract

Asymmetric electrocatalysis offers exciting new strategies for the synthesis of chiral molecules through novel reaction pathways. However, simultaneous activation of reactants on both electrodes via asymmetric paired electrolysis, which is more energy efficient and economic than single half-electrode synthesis, remains a formidable challenge. Herein, an asymmetric olefin−sulfonylimine coupling via paired electrocatalysis is presented for the first time. In this protocol, Co-catalyzed hydrogen atom transfer on the anode and Ni-catalyzed sulfonylimine reduction on the cathode were seamlessly cross-coupled. The new catalytic system enables the formation of chiral amine products bearing a tetrasubstituted carbon stereocenter with a high enantioselectivity (up to 96% ee).

Organoboron-Promoted Electrochemical Chlorosulfonylation of Alkenes with Sulfonyl Chlorides

“…To overcome these issues, metal-catalysts, − redox-mediators, , microfluidic setups, and alternating current electrolysis , have been developed to enhance the stability or diffusion rate of reactive intermediates. Regarding chlorosulfonylation, Lei and co-workers reported a Mn-based catalyst acting as both a redox mediator and chlorine atom transfer reagent to achieve chlorosulfonylation of alkenes and alkynes through convergent paired electrolysis (Scheme B) .…”

Regioselective and Enantioselective Nickel-Catalyzed Intermolecular Reductive Coupling of Aliphatic Alkenes with Imines

“…as well as with alkynes . Moreover, an electrocatalysis strategy was recently reported for enantioselective coupling of vinyl arenes and sulfonylimines . However, enantioselective reductive coupling of imines with readily available unactivated alkenes such as aliphatic alkenes has long been a challenge because of the low reactivity of these alkenes (Scheme B).…”