Suggestion of an organometallic intermediate in an intramolecular dechlorination reaction involving copper(I) and a ArCH2Cl moiety

被引：30

作者：

Maiti, Debabrata ^{[1
]}

Sarjeant, Amy A. Narducci ^{[1
]}

Itoh, Shinobu ^{[2
]}

Karlin, Kenneth D. ^{[1
]}

机构：

[1] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA

[2] Osaka City Univ, Grad Sch Sci, Dept Chem, Sumiyoshi Ku, Osaka 5588585, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 17期

关键词：

D O I：

10.1021/ja800795b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A copper(I)-mediated reductive dechlorination reaction involving an "internal" chloromethylene substrate at the pyridyl 6-position of one TMPA arm (TMPA TPA tris (2-pyridylmethyl)amine) leads to a 1:1 ratio of the starting ligand 6ClCH(2)-TMPA and a new methyl-TMPA product, 6CH(2)H -TMPA. On the basis of observed product distributions and a kinetic study, a reaction mechanism involving intramolecular oxidative insertion of Cu(I) to the C-Cl substrate is suggested. The resulting organometallic intermediate is then protonated, leading to the observed products.

引用

页码：5644 / +

页数：3

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