Chapter 32. The Cationic Rearrangement of (3-Hydroxy-1-Propenyl)tris(trimethylsilyl)silanes into(1-Trimethylsilyl-2-Propenyl)- bis(trimethylsilyl)silanols

  1. Prof. Dr. Norbert Auner2 and
  2. Prof. Dr. Johann Weis3
  1. K. Schmohl,
  2. H. Reinke and
  3. H. Oehme

Published Online: 5 MAY 2008

DOI: 10.1002/9783527619924.ch32

Organosilicon Chemistry V: From Molecules to Materials

Organosilicon Chemistry V: From Molecules to Materials

How to Cite

Schmohl, K., Reinke, H. and Oehme, H. (2003) The Cationic Rearrangement of (3-Hydroxy-1-Propenyl)tris(trimethylsilyl)silanes into(1-Trimethylsilyl-2-Propenyl)- bis(trimethylsilyl)silanols, in Organosilicon Chemistry V: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619924.ch32

Editor Information

  1. 2

    Department of Inorganic Chemistry, University of Frankfurt, Marie-Curie-Straße 11, 60439 Frankfurt am Main, Germany

  2. 3

    Consortium of Electrochemical Industry GmbH, Zielstattstraße 20, 81379 Munich, Germany

Author Information

  1. Fachbereich Chemie der Universität Rostock D-18051 Rostock, Germany Tel: +49 381 498 1765 —Fax: +49 381 498 1763

Publication History

  1. Published Online: 5 MAY 2008
  2. Published Print: 26 SEP 2003

ISBN Information

Print ISBN: 9783527306701

Online ISBN: 9783527619924

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Keywords:

  • silanes;
  • silylcarbenium ions;
  • rearrangements;
  • 1,2-Si,C-trimethylsilyl migration;
  • hypersilyl alcohols

Summary

(3-Hydroxy-1-propenyl)tris(trimethylsilyl)silanes (Me3Si)3Si-CH[DOUBLE BOND]CHC-(OH)R24a-c (a: R = H; b: R = Me; c: R = Ph), made by addition of tris(trimethylsilyl)silane (3) to propargylic alcohol, 2-methyl-3-butyn-2-ol and 1,1-diphenyl-2-propyn-1-ol, respectively, were treated with HCl and H2SO4. Whereas 4a proved to be stable under these conditions, 4b and 4c underwent a rapid isomerization to give the (1-trimethylsilyl-2-propenyl)bis(trimethylsilyl)silanols (Me3Si)2Si(OH)CH(SiMe3)CH[DOUBLE BOND]CR28b and 8c. A possible mechanism of the rearrangement reaction is discussed. Following a similar reaction path, 4b and 4c were converted by boron trifluoride to give the fluorosilanes (Me3Si)2Si(F)CH(SiMe3)CH[DOUBLE BOND]CR2 (10b,c).