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

被引：36
|
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
收藏
页码：9313 / 9318
页数：6
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