Photoelectrochemical iron–cobalt synergistic catalysis for C(sp3)–H alkenylation†

Electrocatalysis and photocatalysis have both emerged as increasingly feasible platforms in sustainable synthesis. This study explores a novel photoelectrochemical synergistic strategy, achieving non-directed C(sp³)–H alkenylation reaction utilizing an iron–cobalt dual catalytic system. With the synergy of photoelectrochemical redox catalysis and iron–cobalt catalysis, efficient C(sp³)–H alkenylation reaction of alkanes as well as dehydrogenation occur without the need for chemical oxidants or reductants, yielding hydrogen gas as the sole byproduct. The electric current is employed to modulate the oxidation states of the catalysts, fulfilling a role similar to that of external oxidants typically used in transition metal catalysis. This method demonstrates unconventional regioselectivity, with a preference for alkenylation at the 1° C–H bonds. This research not only demonstrates that alkenes as radical acceptors can influence the regioselectivity but also offers a promising pathway for advancing iron-catalyzed C–H functionalization.