Enhancing Substrate-Metal Catalyst Affinity via Hydrogen Bonding: Pd(II)-Catalyzed β-C(sp3)-H Bromination of Free Carboxylic Acids

被引：0

作者：

Hu, Liang ^{[1
]}

Meng, Guangrong ^{[1
]}

Chen, Xiangyang ^{[3
]}

Yoon, Joseph S. ^{[2
]}

Shan, Jing-Ran ^{[3
]}

Chekshin, Nikita ^{[1
]}

Strassfeld, Daniel A. ^{[1
]}

Sheng, Tao ^{[1
]}

Zhuang, Zhe ^{[1
]}

Jazzar, Rodolphe ^{[2
]}

Bertrand, Guy ^{[2
]}

Houk, K.N. ^{[3
]}

Yu, Jin-Quan ^{[1
]}

机构：

[1] Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, CA,92037, United States

[2] UCSD-CNRS Joint Research Laboratory (IRL 3555), Department of Chemistry and Biochemistry, University of California, La Jolla, San Diego,CA,92093, United States

[3] Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles,CA,90095, United States

来源：

Journal of the American Chemical Society | 2023年 / 145卷 / 30期

关键词：

Number:; DESC0009376; Acronym:; -; Sponsor:; ACI-1548562; CHE-2153972; NSF; Sponsor: National Science Foundation; NIH; Sponsor: National Institutes of Health; USDOE; Sponsor: U.S. Department of Energy; F32; GM143921; R01GM084019; NIGMS; Sponsor: National Institute of General Medical Sciences; SC; Sponsor: Office of Science; BES; Sponsor: Basic Energy Sciences; Sponsor: Scripps Research Institute; ANR-20-CE07-0000-cResolu; ANR; Sponsor: Agence Nationale de la Recherche;

D O I：

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摘要：

The achievement of sufficient substrate-metal catalyst affinity is a fundamental challenge for the development of synthetically useful C-H activation reactions of weakly coordinating native substrates. While hydrogen bonding has been harnessed to bias site selectivity in existing C(sp2)-H activation reactions, the potential for designing catalysts with hydrogen bond donors (HBDs) to enhance catalyst-substrate affinity and, thereby, facilitate otherwise unreactive C(sp3)-H activation remains to be demonstrated. Herein, we report the discovery of a ligand scaffold containing a remote amide motif that can form a favorable meta-macrocyclic hydrogen bonding interaction with the aliphatic acid substrate. The utility of this ligand scaffold is demonstrated through the development of an unprecedented C(sp3)-H bromination of α-tertiary and α-quaternary free carboxylic acids, which proceeds in exceedingly high mono-selectivity. The geometric relationship between the NHAc hydrogen bond donor and the coordinating quinoline ligand is crucial for forming the meta-macrocyclophane-like hydrogen bonding interaction, which provides a guideline for the future design of catalysts employing secondary interactions. © 2023 American Chemical Society.

引用

页码：16297 / 16304