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Synthesis 2007(19): 3021-3031  
DOI: 10.1055/s-2007-983882
PAPER
© Georg Thieme Verlag Stuttgart · New York

Trimethylsilyl Trifluoromethanesulfonate Catalyzed Nucleophilic Substitution To Give C- and N-Glucopyranosides Derived from d-Glucopyranose

Yoshiki Oda, Takashi Yamanoi*
The Noguchi Institute, 1-8-1 Kaga, Itabashi-ku, Tokyo 173-0003, Japan
e-Mail: tyama@noguchi.or.jp;
Further Information

Publication History

Received 10 May 2007
Publication Date:
11 September 2007 (online)

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Abstract

This paper describes the synthesis of C- and N-glucopyranosides via trimethylsilyl trifluoromethanesulfonate catalyzed nucleophilic substitution of glucopyranosides, derived from d-glucopyranose, with methyl, ethyl, n-butyl, allyl, benzyl, and phenyl groups at the anomeric carbon centers. Generally, the reactions using allyltrimethylsilane, trimethylsilyl azide, trimethylsilyl cyanide, and 1-phenyl-1-(trimethylsiloxy)ethene as the nucleophiles in the presence of 20 mol% trimethylsilyl trifluoromethanesulfonate in acetonitrile­ at -40 °C smoothly proceeded with α-stereoselectivity to afford various C- and N-glucopyranosides in 78-99% yield. Although a decrease in the synthetic yields was observed for some reactions using glucopyranoses with allyl and benzyl groups at the anomeric carbon, the yields could be improved using glucopyranosyl acetates in the presence of 20 mol% trimethylsilyl trifluoro­methanesulfonate in acetonitrile-dichloromethane (1:1) at -78 °C.

Key words

glycosides - nucleophilic substitutions - d-glucopyran­ose - trifluoromethanesulfonate catalysis - trimethylsilylated nucleophiles

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