Visible‐Light Induced C(sp 2 )−H Amidation with an Aryl–Alkyl σ‐Bond Relocation via Redox‐Neutral Radical–Polar Crossover
Autor: | Hyeyun Keum, Hoimin Jung, Jiwoo Jeong, Dongwook Kim, Sukbok Chang |
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Rok vydání: | 2021 |
Předmět: | |
Zdroj: | Angewandte Chemie International Edition. 60:25235-25240 |
ISSN: | 1521-3773 1433-7851 |
Popis: | 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. |
Databáze: | OpenAIRE |
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