Directed Photochemically Mediated Nickel-Catalyzed (Hetero)arylation of Aliphatic C–H Bonds
Site-selective functionalization of unactivated C(sp3)–H centers is challenging because of the ubiquity and strength of alkyl C–H bonds. Herein, we disclose a position-selective C(sp3)–C(sp2) cross-coupling reaction. This process engages C(sp3)–H bonds and aryl bromides, utilizing catalytic quan...
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| Published in: | Journal of the American Chemical Society Vol. 145; no. 7; pp. 3882 - 3890 |
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| Main Authors: | , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
United States
American Chemical Society
22-02-2023
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| Online Access: | Get full text |
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| Summary: | Site-selective functionalization of unactivated C(sp3)–H centers is challenging because of the ubiquity and strength of alkyl C–H bonds. Herein, we disclose a position-selective C(sp3)–C(sp2) cross-coupling reaction. This process engages C(sp3)–H bonds and aryl bromides, utilizing catalytic quantities of a photoredox-capable molecule and a nickel precatalyst. Using this technology, selective C–H functionalization arises owing to a 1,6-hydrogen atom transfer (HAT) process that is guided by a pendant alcohol-anchored sulfamate ester. These transformations proceed directly from N–H bonds, in contrast to previous directed, radical-mediated, C–H arylation processes, which have relied on prior oxidation of the reactive nitrogen center in reactions with nucleophilic arenes. Moreover, these conditions promote arylation at secondary centers in good yields with excellent selectivity. |
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| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 Jennifer L. Roizen – 9432 Collingdale Way, Raleigh, NC 27617, United States Meganathan Nandakumar – Structural Genomics Consortium, UNC Eshelman School of Pharmacy, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-7264, United States R. Thomas Simons – Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH 43210, United States Authors Naresh M. Venneti – Department of Chemistry, Wayne State University, Detroit, MI 48202, United States. All authors have given approval to the final version of the manuscript. M. N. and K.K. contributed equally to this paper. Suraj K. Ayer – TOTUS Medicines, Emeryville, CA 94608, United States Meganathan Nandakumar – Department of Chemistry, Duke University, Durham, NC 27708-0354, United States Present Addresses Suraj K. Ayer – Department of Chemistry, Duke University, Durham, NC 27708-0354, United States R. Thomas Simons – Department of Chemistry, Duke University, Durham, NC 27708-0354, United States Kitae Kwon – Department of Chemistry, Duke University, Durham, NC 27708-0354, United States Author Contributions |
| ISSN: | 0002-7863 1520-5126 1520-5126 |
| DOI: | 10.1021/jacs.2c13409 |