Ligand-Enabled γ-C(sp3)-H Activation of Ketones

被引：115

作者：

Zhu, Ru-Yi ^{[1
]}

Li, Zi-Qi ^{[1
]}

Park, Han Seul ^{[1
]}

Senanayake, Chris H. ^{[2
]}

Yu, Jin-Quan ^{[1
]}

机构：

[1] Scripps Res Inst, Dept Chem, 10550 N Torrey Pines Rd, La Jolla, CA 92037 USA

[2] Boehringer Ingelheim Pharmaceut Inc, Dept Chem Dev, 900 Ridgebury Rd, Ridgefield, CT 06877 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 10期

关键词：

C-H BONDS; CATALYZED INTRAMOLECULAR AMINATION; INTERMOLECULAR AMIDATION; C(SP(3))-H ARYLATION; PALLADIUM; FUNCTIONALIZATION; GAMMA;

D O I：

10.1021/jacs.8b01359

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report the first example of Pd(II)-catalyzed gamma-C(sp(3))-H activation of ketones directed by a practical 2,2-dimethyl aminooxyacetic acid auxiliary. 2-Pyridone ligands are identified to enable C(sp(3))-H activation for the first time. A rare six-membered palladacycle intermediate is isolated and characterized to elucidate the reaction mechanism. Both (hetero)arylation and vinylation of gamma-C(sp(3))-H bonds are demonstrated. Sequential beta- and gamma-C(sp(3))-H (hetero)arylation of muscone showcases the utility of this method for late-stage diversification. A convenient Mn(II)-catalyzed auxiliary removal is also developed to further underscore the practicality of this transformation.

引用

页码：3564 / 3568

页数：5

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