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Synlett 2002(2): 0313-0315
DOI: 10.1055/s-2002-19779
LETTER
© Georg Thieme Verlag Stuttgart · New York

Lewis Acid-catalyzed Reductive Etherification of Carbonyl Compounds with Alkoxyhydrosilanes [1]

Katsukiyo Miura, Kazunori Ootsuka, Shuntaro Suda, Hisashi Nishikori, Akira Hosomi*
Department of Chemistry, Graduate School of Pure and Applied Science, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Fax: +81(298)536503; e-Mail: hosomi@chem.tsukuba.ac.jp;
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Publication History

Received 5 November 2001
Publication Date:
02 February 2007 (online)

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Abstract

The TMSI-catalyzed reaction of aldehydes and ketones with alkoxydimethylsilanes gave unsymmetrical ethers in good to high yields. This reductive etherification is superior to the conventional method using two kinds of silicon reagents in terms of atom efficiency and ease of operation.

Key words

Lewis acids - reductive etherifications - ethers - aldehydes - bifunctional silicon reagents

1

Studies on Organosilicon Chemistry. No. 156.

    References

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1

Studies on Organosilicon Chemistry. No. 156.

10

Alkoxydimethylsilanes 1 were prepared from alcohols, chlorodimethylsilane, and triethylamine (50-60% yield) or from alcohols and(diethylamino)dimethylsilane (50-70% yield).

11

For the formation of dibenzyl ether (reductive dimerization), see ref. [5c] and ref. [6b]

12

General Procedure for the TMSI-catalyzed Reductive Etherification (Method A): To a solution of 1 (1.10 mmol) and a carbonyl compound (1.00 mmol) in CH2Cl2 (1.0 mL) at 0 °C was added TMSI (1.0 M in CH2Cl2, 0.05 mL, 0.05 mmol). The mixture was stirred for 10 min and warmed to r.t. After a given reaction time, the reaction mixture was poured into water (20 mL) and extracted with t-BuOMe (3 × 10 mL). The combined organic layer was dried over Na2SO4 and evaporated. The residual oil was purified by silica gel column chromatography.