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

Michael Andreas Tandiary, Yoichi Masui, Makoto Onaka*

*Graduate School of Arts and Sciences, The University of Tokyo, Meguro-Ku Komaba 3-8-1, Tokyo 153-8902, Japan, Email:

M. A. Tandiary, Y. Masui, M. Onaka, Synlett, 2014, 25, 2639-2643.

DOI: 10.1055/s-0034-1379226 (free Supporting Information)

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The use of sodium ion-exchanged montmorillonite enables a practical and efficient chlorination of benzylic and allylic alcohols. 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.

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Key Words

hydrous sodium montmorillonite, chlorination, benzylic chlorides, allylic chlorides, trimethylsilyl chloride

ID: J60-Y2014