Nitryl Radical‐Triggered Semipinacol‐Type Rearrangement, Lactonization, and Cycloetherification of Olefins
Rahul Giri, Subrata Patra, Dmitry Katayev
Abstract
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 a bench‐stable, non‐metal‐based nitrating reagent. Mechanistic insights suggest that this light‐driven process occurs via NO 2 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.