Metal‐Free Photochemical Olefin Isomerization of Unsaturated Ketones via 1,5‐Hydrogen Atom Transfer
作者:Rajendran Manikandan、Ravindra S. Phatake、N. Gabriel Lemcoff
DOI:10.1002/chem.202200634
日期:2022.5.19
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.
Homo- and cross-coupling involving alkenyl halides have been performed efficiently using an electroassisted nickel-complex catalysis. Valuable product such as conjugated dienes, beta,gamma- or gamma,delta-unsaturated esters, ketones, or nitriles, as well as alkenylated aryl compounds are thus prepared with high yields and high stereoselectivity. Partial isomerization is only observed in a few cases, when the alkenyl halide is involved in a late step of the catalytic cycle. This is the case in the preparation of (Z,Z)-1,3-diene.