Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 144, Issue 18, Pages 8296-8305Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c02392
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Funding
- National Institute of General Medical Sciences (NIGMS)
- NIH [R35GM134897-03]
- Princeton Catalysis Initiative
- BioLec, an Energy Frontier Research Center (U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences) [DE-SC0019370]
- Bristol-Myers Squibb
- NSF [DGE-1656466]
- Princeton University
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In this study, a general catalytic method for direct decarboxylative halogenation of (hetero)aryl carboxylic acids was reported, accommodating an exceptionally broad scope of substrates. The research leveraged an aryl radical intermediate towards two divergent functionalization pathways.
Aryl halides are a fundamental motif in synthetic chemistry, playing a critical role in metal-mediated cross-coupling reactions and serving as important scaffolds in drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope of existing halodecarboxylation methods remains limited, and there currently exists no unified strategy that provides access to any type of aryl halide from an aryl carboxylic acid precursor. Herein, we report a general catalytic method for direct decarboxylative halogenation of (hetero)aryl carboxylic acids via ligand-to-metal charge transfer. This strategy accommodates an exceptionally broad scope of substrates. We leverage an aryl radical intermediate toward divergent functionalization pathways: (1) atom transfer to access bromo- or iodo(hetero)arenes or (2) radical capture by copper and subsequent reductive elimination to generate chloro- or fluoro(hetero)arenes. The proposed ligand-to-metal charge transfer mechanism is supported through an array of spectroscopic studies.
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