Auxiliary-assisted palladium-catalyzed halogenation of unactivated C(sp3)-H bonds at room temperature

被引：59

作者：

Yang, Xinglin ^{[1
]}

Sun, Yonghui ^{[1
]}

Sun, Tian-yu ^{[2
]}

Rao, Yu ^{[1
]}

机构：

[1] Tsinghua Univ, Sch Med, Dept Pharmacol & Pharmaceut Sci, MOE Key Lab Prot Sci, Beijing 100084, Peoples R China

[2] Peking Univ, Shenzhen Grad Sch, Key Lab Chem Genom, Lab Computat Chem & Drug Design, Shenzhen 518055, Peoples R China

来源：

CHEMICAL COMMUNICATIONS | 2016年 / 52卷 / 38期

基金：

中国国家自然科学基金;

关键词：

C-H BONDS; ALPHA-AMINO-ACIDS; INTRAMOLECULAR AMINATION; C(SP(2))-H BONDS; DIRECTING GROUPS; STEREOSELECTIVE-SYNTHESIS; INTERMOLECULAR AMINATION; METHYL-GROUPS; FUNCTIONALIZATION; ACTIVATION;

D O I：

10.1039/c6cc00234j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The direct transformation of unactivated C(sp(3))-H bonds into C-halogen bonds was achieved by palladium catalysis at room temperature with good functional group tolerance. Some drugs and natural products were readily modified by this method. Merged with substitution reaction, newly formed C-X bonds can be transformed into diverse C-O, C-S, C-C and C-N bonds. A preliminary mechanism study demonstrates that solvent is crucial for C-H activation and the C-H activation step is involved in the rate-limiting step. An isolated Pd(II) intermediate can be transformed into a halogenated product with the retention of conformation which suggests that concerted reductive elimination from Pd(IV) to form a C-X bond was favored.

引用

页码：6423 / 6426

页数：4

共 86 条

[21] Palladium-catalyzed asymmetric iodination of unactivated C-H bonds under mild conditions [J].