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
Rok vydání:	2021
Předmět:	chemistry.chemical_classification Trifluoromethyl Aryl General Medicine General Chemistry Photochemistry Redox Catalysis chemistry.chemical_compound chemistry Intramolecular force Photocatalysis Amination Alkyl Visible spectrum
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
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::1ed71418cfc13d2cffd9d3e2f8e80d25 https://doi.org/10.1002/anie.202108775 Zobrazit plný text záznamu Plný text