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. 2021 Nov 22;60(48):25235-25240.
doi: 10.1002/anie.202108775. Epub 2021 Oct 21.

Visible-Light Induced C(sp2 )-H Amidation with an Aryl-Alkyl σ-Bond Relocation via Redox-Neutral Radical-Polar Crossover

Hyeyun Keum  1   2 , Hoimin Jung  1   2 , Jiwoo Jeong  1   2 , Dongwook Kim  1   2 , Sukbok Chang  1   2
Affiliations

Visible-Light Induced C(sp2 )-H Amidation with an Aryl-Alkyl σ-Bond Relocation via Redox-Neutral Radical-Polar Crossover

Hyeyun Keum et al. Angew Chem Int Ed Engl. .

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.

Keywords: amination; lactams; photocatalysis; radical reactions.

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