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Synthesis 2008(23): 3819-3827  
DOI: 10.1055/s-0028-1083219
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

One-Pot Synthesis of α-Siloxy Esters Using a Silylated Masked Acyl Cyanide

Hisao Nemoto*, Rujian Ma, Tomoyuki Kawamura, Kenji Yatsuzuka, Masaki Kamiya, Masayuki Shibuya
Division of Pharmaceutical Chemistry, Institute of Health Biosciences, Graduate School of the University of Tokushima, 1-78 Sho-machi, Tokushima 770-8505, Japan
Fax: +81(88)6337284; e-Mail: nem@ph.tokushima-u.ac.jp;
Further Information

Publication History

Received 22 July 2008
Publication Date:
14 November 2008 (online)

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Abstract

Synthesis of α-siloxy esters via a one-pot reaction from various aldehydes and alcohols using a masked acyl cyanide (MAC) reagent bearing tert-butyldimethylsilyl group is described.

Key words

acyl anion equivalents - masked acyl cyanide - α-hydroxy esters - one-pot - intramolecular migration

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12

The difference in the reaction rate of methanolysis can be reasonably explained as follows. The broad peaks in NMR spectrum of 12b infer a larger steric repulsion between the β-cholesteryl and C-3 side chain moieties of 12b than that of 12a. Thus, the ester bond of 12b was cleaved faster than that of 12a due to the difference of constraint energies of the ester bonds.