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

被引：19

作者：

Hu, Liang ^{[1
]}

Meng, Guangrong ^{[1
]}

Chen, Xiangyang ^{[2
]}

Yoon, Joseph S. S. ^{[3
]}

Shan, Jing-Ran ^{[2
]}

Chekshin, Nikita ^{[1
]}

Strassfeld, Daniel A. A. ^{[1
]}

Sheng, Tao ^{[1
]}

Zhuang, Zhe ^{[1
]}

Jazzar, Rodolphe ^{[3
]}

Bertrand, Guy ^{[3
]}

Houk, K. N. ^{[2
]}

Yu, Jin-Quan ^{[1
]}

机构：

[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA

[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[3] Univ Calif San Diego, Dept Chem & Biochem, UCSD CNRS Joint Res Lab IRL 3555, La Jolla, CA 92093 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2023年 / 145卷 / 30期

基金：

美国国家科学基金会;

关键词：

C-H ACTIVATION; NONCOVALENT INTERACTIONS; LIGAND; IODINATION; BORYLATION;

D O I：

10.1021/jacs.3c04223

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The achievement of sufficient substrate-metalcatalyst affinityis a fundamental challenge for the development of synthetically usefulC-H activation reactions of weakly coordinating native substrates.While hydrogen bonding has been harnessed to bias site selectivityin existing C(sp(2))-H activation reactions, the potentialfor designing catalysts with hydrogen bond donors (HBDs) to enhancecatalyst-substrate affinity and, thereby, facilitate otherwiseunreactive C(sp(3))-H activation remains to be demonstrated.Herein, we report the discovery of a ligand scaffold containing aremote amide motif that can form a favorable meta-macrocyclic hydrogen bonding interaction with the aliphatic acidsubstrate. The utility of this ligand scaffold is demonstrated throughthe development of an unprecedented C(sp(3))-H brominationof & alpha;-tertiary and & alpha;-quaternary free carboxylic acids,which proceeds in exceedingly high mono-selectivity.The geometric relationship between the NHAc hydrogen bond donor andthe coordinating quinoline ligand is crucial for forming the meta-macrocyclophane-like hydrogen bonding interaction,which provides a guideline for the future design of catalysts employingsecondary interactions.

引用

页码：16297 / 16304

页数：8

共 47 条

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