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Stereochemistry in Lewis acid-catalyzed silylation of alcohols, silanols, and methoxysilanes with optically active methyl(1-naphthyl)phenylsilane

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Silicon Chemistry

Abstract

Stereochemistry in silylation reactions of alcohols, silanols, and methoxysilanes with optically pure (R)-methyl(1-naphthyl)phenylsilane were studied in the presence of Lewis acid catalysts. Tris(pentafluorophenyl)borane [B(C6F5)3] was found to be highly reactive and stereoselective in the reactions. Optically active (R)-(alkoxy)methyl(1-naphthyl)phenylsilanes with 91–97% ee were produced from alcohols through the inversion stereochemistry of the silane. Stereoselectivity in the reaction with triphenylsilanol was moderate (64% ee). (R)-1,3-Dimethyl-1-(1-naphthyl)-1,3,3-triphenyldisiloxane with 94% ee was obtained from the silane with (methoxy)methyldiphenylsilane. The reaction with (R)-(methoxy)methyl(1-naphthyl)phenylsilane (88% ee) gave (R, R)-1,3-dimethyl-1,3-di(1-naphthyl)-1,3-diphenyldisiloxane [(R, R):(R, S):(S, S) = 87:12:0.5]. The stereochemistry was proved to almost completely inversion and retention for the chiral silicon centers of the silane and methoxysilane, respectively.

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Authors and Affiliations

  1. School of Materials Science, Japan Advanced Institute of Science and Technology, Asahidai 1-1, Nomi, Ishikawa, 923-1292, Japan

    Satoshi Shinke, Teruhisa Tsuchimoto & Yusuke Kawakami

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  1. Satoshi Shinke
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  2. Teruhisa Tsuchimoto
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  3. Yusuke Kawakami
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Correspondence to Yusuke Kawakami.

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Shinke, S., Tsuchimoto, T. & Kawakami, Y. Stereochemistry in Lewis acid-catalyzed silylation of alcohols, silanols, and methoxysilanes with optically active methyl(1-naphthyl)phenylsilane. Silicon Chem 3, 243–249 (2007). https://doi.org/10.1007/s11201-007-9026-y

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  • DOI: https://doi.org/10.1007/s11201-007-9026-y

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