Metal‐Free Photochemical Olefin Isomerization of Unsaturated Ketones via 1,5‐Hydrogen Atom Transfer

The photochemical isomerization of α,β‐ to β,γ‐unsaturated ketones through a 1,5‐hydrogen atom transfer mechanism under mild conditions with high efficiency and selectivity is reported. The reaction is carried out in the absence of metal catalysts or other additives, and its stereoselectivity can be tuned by selecting appropriate solvent mixtures. The reaction‘s scope and tolerance towards functional groups, including light‐sensitive halogens, free acids and alcohols, were studied, providing reliable access to a wide variety of β,γ‐unsaturated ketones. This methodology details the deconjugation of a wide range of unsaturated ketones and, when combined with olefin metathesis, provides an efficient process for either dehomologation or one‐carbon double‐bond migration of terminal alkenes. Bring on the Light: An efficient photochemical metal/catalyst‐free system has been uncovered for the selective one‐bond olefin migration of unsaturated ketones. Diverse substrate scope, functional group tolerance and its application for dehomologation and one‐carbon selective olefin migration processes in linear alkenes highlights the usefulness of this method.