Palladium-Catalyzed Intramolecular C-H Arylation versus 1,5-Palladium Migration: A Theoretical Investigation

被引：18
|
作者：
Misawa, Nana [1 ]
Tsuda, Tomohiro [2 ]
Shintani, Ryo [2 ]
Yamashita, Koichi [3 ]
Nozaki, Kyoko [1 ]
机构：
[1] Univ Tokyo, Grad Sch Engn, Dept Chem & Biotechnol, Bunkyo Ku, 7-3-1 Hongo, Tokyo 1138656, Japan
[2] Osaka Univ, Grad Sch Engn Sci, Div Chem, Dept Mat Engn Sci, Toyonaka, Osaka 5608531, Japan
[3] Univ Tokyo, Sch Engn, Dept Chem Syst Engn, Bunkyo Ku, 7-3-1 Hongo, Tokyo 1138656, Japan
来源：
CHEMISTRY-AN ASIAN JOURNAL | 2018年 / 13卷 / 17期
关键词：
arylation; chemoselectivity; density functional calculations; C-H activation; palladium; DENSITY-FUNCTIONAL THEORY; ASYMMETRIC-SYNTHESIS; 1,4-PALLADIUM MIGRATION; BOND ACTIVATION; EFFICIENT SYNTHESIS; AROMATIC RINGS; ARYL BROMIDES; RHODIUM; CYCLIZATION; COMPLEXES;
D O I：
10.1002/asia.201800603
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Theoretical investigations were carried out to elucidate the origin of chemoselectivity in the palladium-catalyzed reactions of 2-(dimethylphenylsilyl)phenyl triflates with or without an amino group at the 3-position. The selective formation of a 5,10-dihydrophenazasiline rather than a dibenzosilole from the substrate with an amino group at the 3-position could be successfully explained by proposing a new 1,5-palladium migration pathway that involves a neutral diorganopalladium(II) intermediate along with the subsequent formation of a low-energy amine-coordinated palladacycle intermediate prior to the C-N bond-forming process.
引用
收藏
页码：2566 / 2572
页数：7
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