Issue 15, 2008
From the journal:

Organic & Biomolecular Chemistry

Direct chlorination of alcohols with chlorodimethylsilane catalyzed by a gallium trichloride/tartrate system under neutral conditions†

Makoto Yasuda,a   Kenji Shimizu,a   Satoshi Yamasakia  and  Akio Baba*a  

* Corresponding authors

a Department of Applied Chemistry and Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, Japan
E-mail: yasuda@chem.eng.osaka-u.ac.jp
Fax: +81 6-6879-7387
Tel: +81 6-6879-7386

Abstract

The reaction of secondary alcohols 1 with chlorodimethylsilane (HSiMe2Cl) proceeded in the presence of a catalytic amount of GaCl3/diethyl tartrate to give the corresponding organic chlorides 3. In the catalytic cycle, the reaction of diethyl tartrate 4a with HSiMe2Cl 2 gives the chlorosilyl ether 5 with generation of H2. Alcohol-exchange between the formed chlorosilyl ether 5 and the substrate alcohol 1 affords alkoxychlorosilane 6, which reacts with catalytic GaCl3 to give the chlorinated product 3. The moderate Lewis acidity of GaCl3 facilitates chlorination. Strong Lewis acids did not give product due to excessive affinity for the oxy-functionalities. Although tertiary alcohols were chlorinated by this system even in the absence of diethyl tartrate, certain alcohols that are less likely to give carbocationic species were effectively chlorinated using the GaCl3/diethyl tartrate system.

Graphical abstract: Direct chlorination of alcohols with chlorodimethylsilane catalyzed by a gallium trichloride/tartrate system under neutral conditions

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Article information

DOI
https://doi.org/10.1039/B804589E
Article type
Paper
Submitted
17 Mar 2008
Accepted
18 Apr 2008
First published
28 May 2008

Org. Biomol. Chem., 2008,6, 2790-2795

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Direct chlorination of alcohols with chlorodimethylsilane catalyzed by a gallium trichloride/tartrate system under neutral conditions

M. Yasuda, K. Shimizu, S. Yamasaki and A. Baba, Org. Biomol. Chem., 2008, 6, 2790 DOI: 10.1039/B804589E

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