Cobalt‐Catalyzed Intramolecular Markovnikov Hydrocarbonylation of Unactivated Alkenes via Hydrogen Atom Transfer

Abstract A cobalt‐catalyzed intramolecular Markovnikov hydroalkoxycarbonylation and hydroaminocarbonylation of unactivated alkenes has been developed, enabling highly chemo‐ and regioselective synthesis of α ‐alkylated γ ‐lactones and α ‐alkylated γ ‐lactams in good yields. The mild reaction conditions allow use of mono‐, di‐ and trisubstituted alkenes bearing a variety of functional groups. Preliminary mechanistic studies suggest the reaction proceeds through a CO‐mediated hydrogen atom transfer (HAT) and radical‐polar crossover (RPC) process, in which a cationic acylcobalt(IV) complex is proposed as the key intermediate.