Synlett 2014; 25(18): 2639-2643
DOI: 10.1055/s-0034-1379226
letter
© Georg Thieme Verlag Stuttgart · New York

Chlorination of Benzylic and Allylic Alcohols with Trimethylsilyl Chloride Enhanced by Natural Sodium Montmorillonite

Michael Andreas Tandiary
a   Department of Chemistry, Graduate School of Sciences, The University of Tokyo, Bunkyo-Ku Hongo 7-3-1, Tokyo 113-0033, Japan
,
Yoichi Masui
b   Graduate School of Arts and Sciences, The University of Tokyo, Meguro-Ku Komaba 3-8-1, Tokyo 153-8902, Japan   Fax: +81(3)54546998   Email: conaka@mail.ecc.u-tokyo.ac.jp
,
Makoto Onaka*
b   Graduate School of Arts and Sciences, The University of Tokyo, Meguro-Ku Komaba 3-8-1, Tokyo 153-8902, Japan   Fax: +81(3)54546998   Email: conaka@mail.ecc.u-tokyo.ac.jp
› Author Affiliations
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Publication History

Received: 30 July 2014

Accepted after revision: 08 September 2014

Publication Date:
15 October 2014 (online)


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Abstract

A new and practical method for the efficient chlorination of tertiary, secondary, and primary benzylic and allylic alcohols is described. The method is characterized by the formation of hydrogen chloride from trimethylsilyl chloride and trace water, the formation of a carbenium ion through the protonation of an alcohol and subsequent dehydration, and the chlorination of the carbenium ion. During the process, sodium ion-exchanged montmorillonite plays a crucial role in capturing the generated hydrogen chloride, stabilizing the carbenium intermediate as well as promoting the chlorination.

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