Harnessing Diazo Compounds as Alkoxycarbonyl Methylene Radical Linchpins: Truce–Smiles Rearrangement toward Amido Esters and Isoquinolinedione Scaffolds
Abstract
Abstract The radical reactivity of acceptor-type diazo compounds is harnessed in the photochemical Truce–Smiles rearrangement of N-aryl-N-arylsulfonyl acrylamides to access β,β′-disubstituted amido esters. The rational design of starting materials and the cascade technique can be extended to yield isoquinolinediones to display atropisomerism. Mechanistic investigations support a radical-mediated proton-coupled electron transfer (PCET) process involving intramolecular migration of an aryl radical via a spiro intermediate. This protocol shows the untapped potential of diazo chemistry for radical-based transformations beyond traditional carbene pathways.
Fields of Study & Subjects
Radical Photochemical Reactions
Cyclopropane Reaction Mechanisms
Catalytic C–H Functionalization Methods
Publication details
- Journal / source
- Organic Letters
- Publisher
- American Chemical Society (ACS)
- Volume
- 28
- Issue
- 37
- Pages
- 11757–11762
- Publication date
- 3 September 2026
- Language
- EN