@article{0f5be854b4b240e8a83ad066176e4d53,
title = "A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids",
abstract = "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.",
author = "Chen, {Tiffany Q.} and Pedersen, {P. Scott} and Dow, {Nathan W.} and Remi Fayad and Hauke, {Cory E.} and Rosko, {Michael C.} and Danilov, {Evgeny O.} and Blakemore, {David C.} and Dechert-Schmitt, {Anne Marie} and Thomas Knauber and Castellano, {Felix N.} and Macmillan, {David W.C.}",
note = "Funding Information: The authors are grateful for financial support provided by the National Institute of General Medical Sciences (NIGMS), the NIH (under Award R35GM134897-03), the Princeton Catalysis Initiative, BioLec, an Energy Frontier Research Center (U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0019370), and kind gifts from Pfizer, Merck, Janssen, Bristol-Myers Squibb, and Genentech. T.Q.C. thanks Bristol-Myers Squibb for a graduate fellowship. P.S.P. thanks the NSF for a predoctoral fellowship (Award DGE-1656466). N.W.D. thanks Princeton University, E.C. Taylor and the Taylor family for support via the Edward C. Taylor fellowship. The content is solely the responsibility of the authors and does not necessarily represent the official views of NIGMS. This work was performed in part at the Laboratory for Imaging and Kinetic Spectroscopy at North Carolina State University. The authors thank Rebecca Lambert for assistance in the preparation of this manuscript. Publisher Copyright: {\textcopyright} ",
year = "2022",
doi = "10.1021/jacs.2c02392",
language = "English (US)",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
}