Scaleable Preparation of Sensitive Functionalized Aromatics and Heteroaromatics via Directed Metalation Using tmpZnCl•LiCl

被引：30

作者：

Bresser, Tomke ^{[1
]}

Monzon, Gabriel ^{[1
]}

Mosrin, Marc ^{[1
]}

Knochel, Paul ^{[1
]}

机构：

[1] Univ Munich, Dept Chem, D-81377 Munich, Germany

来源：

ORGANIC PROCESS RESEARCH & DEVELOPMENT | 2010年 / 14卷 / 06期

基金：

欧洲研究理事会;

关键词：

CHEMOSELECTIVE MULTIPLE FUNCTIONALIZATION; MEDIATED MANGANATION(II); DEPROTONATIVE METALATION; PYRIMIDINE-DERIVATIVES; POLYFUNCTIONAL ARYL; DIAZINES PYRIDINES; ZINCATION; MAGNESIATION; ARENES; HETEROCYCLES;

D O I：

10.1021/op1001935

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

A range of functional aryl and heteroaryl zinc reagents were prepared in THF via directed zincation using the previously reported amide base tmpZnCl center dot LiCl. These metalation reactions were carried out on 50 mmol scale. Diverse sensitive functional groups such as a nitro group, an aldehyde, an ester, and a nitrile are tolerated. Furthermore, the resulting zinc intermediates show excellent reactivity towards various classes of electrophiles, e.g. Pd-catalyzed cross-coupling reactions or Cu-catalyzed acylations and allylations. In all cases, the metalation rates have been compared with those of the corresponding small-scale reactions (1-2 mmol). Moreover, the recovery of the valuable tmp-H from the aqueous phase has been demonstrated.

引用

收藏

页码：1299 / 1303

页数：5

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