دورية أكاديمية
A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids.
| العنوان: | A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids. |
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| المؤلفون: | Chen TQ; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States., Pedersen PS; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States., Dow NW; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States., Fayad R; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, United States., Hauke CE; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, United States., Rosko MC; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, United States., Danilov EO; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, United States., Blakemore DC; Worldwide Research and Development, Pfizer, Inc., Eastern Point Road, Groton, Connecticut 06340, United States., Dechert-Schmitt AM; Worldwide Research and Development, Pfizer, Inc., Eastern Point Road, Groton, Connecticut 06340, United States., Knauber T; Worldwide Research and Development, Pfizer, Inc., Eastern Point Road, Groton, Connecticut 06340, United States., Castellano FN; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, United States., MacMillan DWC; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States. |
| المصدر: | Journal of the American Chemical Society [J Am Chem Soc] 2022 May 11; Vol. 144 (18), pp. 8296-8305. Date of Electronic Publication: 2022 Apr 29. |
| نوع المنشور: | Journal Article; Research Support, U.S. Gov't, Non-P.H.S.; Research Support, N.I.H., Extramural; Research Support, Non-U.S. Gov't |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: MEDLINE |
| أسماء مطبوعة: | Publication: Washington, DC : American Chemical Society Original Publication: Easton, Pa. [etc.] |
| مواضيع طبية MeSH: | Carboxylic Acids*/chemistry , Halogenation*, Catalysis ; Copper/chemistry ; Ligands |
| مستخلص: | 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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| معلومات مُعتمدة: | R35 GM134897 United States GM NIGMS NIH HHS |
| المشرفين على المادة: | 0 (Carboxylic Acids) 0 (Ligands) 789U1901C5 (Copper) |
| تواريخ الأحداث: | Date Created: 20220429 Date Completed: 20220512 Latest Revision: 20221121 |
| رمز التحديث: | 20231215 |
| مُعرف محوري في PubMed: | PMC9676088 |
| DOI: | 10.1021/jacs.2c02392 |
| PMID: | 35486956 |
| قاعدة البيانات: | MEDLINE |
Find this issue from the American Chemical Society | تدمد: | 1520-5126 |
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| DOI: | 10.1021/jacs.2c02392 |