Nitryl Radical‐Triggered Semipinacol‐Type Rearrangement, Lactonization, and Cycloetherification of Olefins

Abstract We report the development of a practical photocatalytic strategy to access various nitro‐containing cyclic compounds from olefins via semipinacol‐type rearrangement, cycloetherification, and lactonization reactions, employing N ‐nitrosuccinimide as bench‐stable, non‐metal‐based nitrating reagent. Mechanistic insights suggest that this light‐driven process occurs NO 2 radical pathway mediated by photoredox catalyst, which triggers an N−N bond fragmentation. Subsequent Giese‐type addition nitryl radicals activated takes place, leading formation β ‐functionalized ketones, lactones cycloethers. The reaction proceeds under mild conditions tolerates wide range functional groups structural variations.