N-Aryl Groups Are Ubiquitous in Cross-Dehydrogenative Couplings Because They Stabilize Reactive Intermediates

被引：34

作者：

Tsang, Althea S. -K. ^{[1
]}

Hashmi, A. Stephen K. ^{[2
,3
]}

Comba, Peter ^{[4
]}

Kerscher, Marion ^{[4
]}

Chan, Bun ^{[1
,5
]}

Todd, Matthew H. ^{[1
]}

机构：

[1] Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia

[2] Heidelberg Univ, Inst Organ Chem, Neuenheimer Feld 270, D-69120 Heidelberg, Germany

[3] King Abdulaziz Univ, Fac Sci, Chem Dept, Jeddah 21589, Saudi Arabia

[4] Heidelberg Univ, Inst Inorgan Chem, Neuenheimer Feld 270, D-69120 Heidelberg, Germany

[5] Nagasaki Univ, Grad Sch Engn, Bunkyo 1-14, Nagasaki 8528521, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2017年 / 23卷 / 39期

关键词：

amines; C-C coupling; cross-coupling; mechanistic studies; radicals; SP(3) C-H; MANNICH-TYPE REACTION; HIGHLY EFFICIENT; ELECTRON-TRANSFER; HYDRIDE TRANSFER; BOND-CLEAVAGE; METAL-FREE; OXIDATION; IRON; FUNCTIONALIZATION;

D O I：

10.1002/chem.201700430

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of cross-dehydrogenative coupling (CDC) reactions has been examined by experimental and computational methods. We provide a rationale for the ubiquity of the N-aryl group in these reactions. The aryl substituent stabilizes two intermediates and the high-energy transition state that connects them, which together represent the rate-determining step. This knowledge has enabled us to predict whether new CDC substrates will react either well or poorly.

引用

页码：9313 / 9318

页数：6

共 24 条

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