Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 19, Pages 10690-10699Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202100949
Keywords
bimetallic catalysts; carboxylic acids; C-O/C-H bond activation; decarbonylation; heteroarylation
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Funding
- NIH [1R35GM133326]
- NSF [CAREER CHE-1650766]
- Rutgers University
- NSFC [21702182, 21873081]
- Fundamental Research Funds for the Central Universities
- Zhejiang University
- NSF-MRI [CHE-1229030]
- Rutgers Graduate School
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Cooperative bimetallic catalysis was used in the direct decarbonylative heteroarylation of carboxylic acids, enabling synthesis of important heterobiaryl motifs with high chemoselectivity. This method, which does not require prefunctionalization or directing groups, has a broad substrate scope and shows potential for late-stage modification of pharmaceuticals and streamlined synthesis of bioactive agents. Extensive mechanistic and computational studies were conducted to understand the reaction mechanism, identifying a key step involving the intersection of two catalytic cycles.
Cooperative bimetallic catalysis is a fundamental approach in modern synthetic chemistry. We report bimetallic cooperative catalysis for the direct decarbonylative heteroarylation of ubiquitous carboxylic acids via acyl C-O/C-H coupling. This novel catalytic system exploits the cooperative action of a copper catalyst and a palladium catalyst in decarbonylation, which enables highly chemoselective synthesis of important heterobiaryl motifs through the coupling of carboxylic acids with heteroarenes in the absence of prefunctionalization or directing groups. This cooperative decarbonylative method uses common carboxylic acids and shows a remarkably broad substrate scope (>70 examples), including late-stage modification of pharmaceuticals and streamlined synthesis of bioactive agents. Extensive mechanistic and computational studies were conducted to gain insight into the mechanism of the reaction. The key step involves intersection of the two catalytic cycles via transmetallation of the copper-aryl species with the palladium(II) intermediate generated by oxidative addition/decarbonylation.
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