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

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 a bench‐stable, non‐metal‐based nitrating reagent. Mechanistic insights suggest that this light‐driven process occurs via NO2 radical pathway mediated by a photoredox catalyst, which triggers an N−N bond fragmentation. Subsequent Giese‐type addition of nitryl radicals to activated olefins takes place, leading to the formation of nitro‐containing β‐functionalized ketones, lactones and cycloethers. The reaction proceeds under mild reaction conditions and tolerates a wide range of functional groups and structural variations. [ABSTRACT FROM AUTHOR]