cis‐Selective Transfer Semihydrogenation of Alkynes by Merging Visible‐Light Catalysis with Cobalt Catalysis

Herein, the first example of visible‐light‐driven, cobalt‐catalyzed transfer semihydrogenation of alkynes to alkenes is reported. It is carried out by using Ir[dF(CF3)ppy]2(dtbbpy)]PF6 as photosensitizer, CoBr2/n‐Bu3P as proton‐reducing catalyst, and i‐Pr2NEt/AcOH as the hydrogen source. Under the established catalytic system, the semihydrogenation proceeds with Z as the major selectivity and with inhibition of over‐reduction. Under mild reaction conditions, both internal and terminal alkynes, as well as reducible functional groups such as halogen, cyano, and ester, are tolerated. Preliminary mechanistic studies revealed the dual role of the photosensitizer in initiating the reaction via a single‐electron transfer process and controlling the stereoselectivity via an energy transfer process.