Asymmetric Remote meta-C-H Activation Controlled by a Chiral Ligand

被引：0

作者：

Wang, Hang ^{[1
]}

Li, Huiling ^{[2
]}

Chen, Xiahe ^{[2
]}

Zhou, Chunlin ^{[1
]}

Li, Shangda ^{[1
]}

Yang, Yun-Fang ^{[2
]}

Li, Gang ^{[1
,3
]}

机构：

[1] Chinese Acad Sci, Fujian Inst Res Struct Matter, Key Lab Coal Ethylene Glycol & Its Related Technol, Fuzhou 350002, Fujian, Peoples R China

[2] Zhejiang Univ Technol, Coll Chem Engn, Hangzhou 310014, Zhejiang, Peoples R China

[3] Shanghai Jiao Tong Univ, Frontiers Sci Ctr Transformat Mol, Sch Chem & Chem Engn, Shanghai Key Lab Mol Engn Chiral Drugs, Shanghai 200240, Peoples R China

来源：

ACS CATALYSIS | 2022年 / 12卷 / 21期

关键词：

KEYWORDS; asymmetric remote C; H activation; ligand-controlled; meta; -selective; olefination; arylation; palladium catalysis; TRACELESS DIRECTING GROUPS; ENANTIOSELECTIVE SYNTHESIS; SITE-SELECTIVITY; CARBOXYLIC-ACIDS; BOND ACTIVATION; AMINO-ACIDS; FUNCTIONALIZATION; BORYLATION; ALKYLATION; ARYLATION;

D O I：

10.1021/acscatal.2c0318713435

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The use of a chiral ligand for stereocontrol has assisted the development of a number of asymmetric functionalization of proximal C-H bonds. Herein, we report a chiral ligand-controlled, asymmetric remote meta-C-H activation of arenes, leading to asymmetric C-H olefination and arylation of hydrocinnamic acid derivatives through desymmetrization with Ac-L-Phe-OH as the chiral ligand using a Pd(II) catalyst. The origins of the enantioselectivity were explained with density functional theory calculations. The larger distortion energy of the substrate part in the C-H bond activation transition structure S-TS1 is the major controlling factor that disfavors the formation of the S-enantiomer product.

引用

页码：13435 / 13445

页数：11