Deconjugative Photoisomerization of Cyclic Enones

The deconjugative isomerization of α,β-unsaturated carbonyl compounds enables regioisomeric products to be forged with simultaneous Umpolung of alkene reactivity. Although highly enabling, the endergonic nature of the net process coupled with governing regioselectivity outcomes, renders it challenging. Innovations in the positional isomerization of linear species, often by light-triggered activation, have re-energized this area. However, the deconjugative isomerization of cyclic enones is underdeveloped and often associated with impractical reaction conditions, limited substrate scopes, and a lack of mechanis-tic clarity. Herein, we report an operationally simple photochemical isomerization of cyclic enones using near-UV (372 nm) irradiation with catalytic amounts of Brønsted acid (HCl). This platform enables exocyclic deconjugative isomerization of a diverse array of enones including α-isophorone (a key intermediate in a variety of industrial processes), terpenoids and ster-oids. Mechanistic studies reveal the pivotal role of the solvent as a key mediator in the isomerization, where sequential hy-drogen atom transfer (HAT) and reverse-HAT (RHAT) are proposed to be operational.