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Updated: Oct 19, 2025

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Visible-Light Induced C(sp2 )-H Amidation with an Aryl-Alkyl σ-Bond Relocation via Redox-Neutral Radical-Polar
Hyeyun Keum1,2, Hoimin Jung1,2, Jiwoo Jeong1,2
1Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Republic of Korea.
Abstract:
We report an approach for the intramolecular C(sp2 )-H amidation of N-acyloxyamides under photoredox conditions to produce δ-benzolactams with an aryl-alkyl σ-bond relocation. Computational studies on the designed reductive single electron transfer strategy led us to identify N-[3,5-bis(trifluoromethyl)benzoyl] group as the most effective amidyl radical precursor. Upon the formation of an azaspirocyclic radical intermediate by the selective ipso-addition with outcompeting an ortho-attack, radical-polar crossover was then rationalized to lead to the rearomative ring-expansion with preferential C-C bond migration.
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