Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 51, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202213943
Keywords
2, 2'-Bipyridine Ligands; Asymmetric Catalysis; Carboxylation; Enantioselectivity; Nickel Catalysis
Categories
Funding
- NSFC
- Shaanxi Provincial Science and Technology Department
- China Postdoctoral Science Foundation
- Chung Ying Scholar of XJTU
- [22171218]
- [21971202]
- [22150410339]
- [2020JC-08]
- [BX20220252]
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A nickel-catalyzed general, efficient, and highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides has been developed, utilizing atmospheric CO2 under mild conditions. A unique chiral 2,2'-bipyridine ligand enabled both high reactivity and stereoselectivity.
In contrast to previous approaches to chiral alpha-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 alpha-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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