Redox-Gated Tertiary Allylic C–H Oxygenation via Photocatalytic Radical-Polar Crossover
Abstract
We developed a photoredox strategy for the highly regioselective oxygenation of tertiary allylic and propargylic C-H bonds with alcohols or water nucleophiles. The reaction proceeds via a redox-gated radical-polar-crossover pathway, in which intermolecular hydrogen atom transfer generates allylic radicals that are selectively oxidized to carbocations only at tertiary sites, enabling a subsequent C-O bond formation by trapping with oxygen nucleophiles. This approach overrides the inherent preference for less hindered positions in classical metal-catalyzed π-allyl chemistry. The method accommodates internal alkenes, alkynes, and diverse alcohol nucleophiles, including complex bioactive substrates, and enables both intermolecular and intramolecular modes of oxygenation.
Fields of Study & Subjects
Radical Photochemical Reactions
Catalytic C–H Functionalization Methods
Oxidative Organic Chemistry Reactions
Publication details
- Journal / source
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Volume
- 148
- Issue
- 27
- Pages
- 28010–28018
- Publication date
- 30 June 2026
- Language
- EN