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

页码：2566 / 2572

页数：7

共 50 条

[21] Twofold C-H functionalization:: Palladium-catalyzed ortho arylation of anilides
Brasche, Gordon
Garcia-Fortanet, Jorge
Buchwald, Stephen L.
ORGANIC LETTERS, 2008, 10 (11) : 2207 - 2210
[22] Palladium-catalyzed direct C-H arylation of ferrocenecarboxamides with aryl halides
Qiao, Huijie
Sun, Suyan
Yang, Fan
Zhu, Yu
Zhu, Weiguo
Wu, Yusheng
Wu, Yangjie
RSC ADVANCES, 2016, 6 (64) : 59319 - 59326
[23] Palladium-Catalyzed Direct C-H Arylation of Enamides with Simple Arenes
Pankajakshan, Sreekumar
Xu, Yun-He
Cheng, Jun Kee
Low, Man Ting
Loh, Teck-Peng
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (23) : 5701 - 5705
[24] Palladium-catalyzed desulfitative C-H arylation of azoles with sodium sulfinates
Chen, Ru
Liu, Saiwen
Liu, Xinhua
Yang, Luo
Deng, Guo-Jun
ORGANIC & BIOMOLECULAR CHEMISTRY, 2011, 9 (22) : 7675 - 7679
[25] Palladium-Catalyzed C-H Arylation of Indoles at the C7 Position
Shi, Zhuangzhi (shiz@nju.edu.cn), 1600, American Chemical Society (138):
[26] Palladium-Catalyzed C-H Arylation of Indoles at the C7 Position
Yang, Youqing
Qiu, Xiaodong
Zhao, Yue
Mu, Yucheng
Shi, Zhuangzhi
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (02) : 495 - 498
[27] Palladium-catalyzed C-H arylation of indoles at the C7 position
Science Foundation in China, 2016, (03) : 32 - 32
[28] Intramolecular C-H activation by alkylpalladium(II) complexes:: Insights into the mechanism of the palladium-catalyzed arylation reaction
Martín-Matute, B
Mateo, C
Cárdenas, DJ
Echavarren, AM
CHEMISTRY-A EUROPEAN JOURNAL, 2001, 7 (11) : 2341 - 2348
[29] Intramolecular benzylic C-H activation: palladium-catalyzed synthesis of hexahydromethanofluorenes
Catellani, M
Motti, E
Ghelli, S
CHEMICAL COMMUNICATIONS, 2000, (20) : 2003 - 2004
[30] Fluoradenes via palladium-catalyzed intramolecular arylation
Rong, Lingling
Liu, Qiancai
Shi, Yingbo
Tang, Jie
CHEMICAL COMMUNICATIONS, 2011, 47 (07) : 2155 - 2157

← 1 2 3 4 5 →