Photo‐ and Cobalt‐Catalyzed Synthesis of Heterocycles via Cycloisomerization of Unactivated Olefins

We report a general, intramolecular cycloisomerization of unactivated olefins with pendant nucleophiles. The reaction proceeds under mild conditions and tolerates ethers, esters, protected amines, acetals, pyrazoles, carbamates, and arenes. It is amenable to N‐, O‐, as well as C‐nucleophiles, yielding a number of different heterocycles including, but not limited to, pyrrolidines, piperidines, oxazolidinones, and lactones. Use of both a benzothiazinoquinoxaline as organophotocatalyst and a Co‐salen catalyst obviates the need for stoichiometric oxidant or reductant. We showcase the utility of the protocol in late‐stage drug diversification and synthesis of several small natural products.