Nickel-Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2'-Bipyridine Ligand.
Angew Chem Int Ed Engl
; 61(51): e202213943, 2022 12 19.
Article
en En
| MEDLINE
| ID: mdl-36300599
ABSTRACT
In contrast to previous approaches to chiral α-aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel-catalyzed general, efficient and highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions using atmospheric CO2 has been developed. A unique chiral 2,2'-bipyridine ligand named Me-SBpy featuring compact polycyclic skeleton enabled both high reactivity and stereoselectivity. The utility of this method has been demonstrated by synthesis of various chiral α-aryl carboxylic acids (30 examples, up to 95 % yield and 99 1 er), including profen family anti-inflammatory drugs and transformations using the acids as key intermediates. Based on mechanistic experimental results, a plausible catalytic cycle involving Ni-complex/radical equilibrium and Lewis acid-assisted CO2 activation has been proposed.
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Texto completo:
1
Colección:
01-internacional
Banco de datos:
MEDLINE
Asunto principal:
Compuestos Heterocíclicos
/
Níquel
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2022
Tipo del documento:
Article
País de afiliación:
China