Synlett 2003(12): 1940-1941
DOI: 10.1055/s-2003-41457
SPOTLIGHT
© Georg Thieme Verlag Stuttgart · New York

Trimethylsilyl Trifluoromethanesulfonate (TMSOTf)

William R. F. Goundry*
The Dyson Perrins Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QY, UK
e-Mail: william.goundry@queens.ox.ac.uk;
Further Information

Publication History

Publication Date:
19 September 2003 (online)

Introduction

The title compound is a colourless, mobile liquid, which dissolves in aliphatic or aromatic hydrocarbons and haloalkanes without any reaction. [1] Due to the presence of the electron-withdrawing trifluoromethanesulfonyl moiety the silicon atom is extremely electron deficient. Subsequently the silicon atom reacts with heteroatoms, especially oxygen to form onium ions. In contrast to more conventional Lewis acids such as AlCl3 and TiCl4, TMSOTf tends to bind to a single hetero functional group. TMSOTf is 6.7 × 108 times more reactive than TMSCl, and this is manifested in an extreme sensitivity towards moisture which must be excluded from all reactions. [2] The ability of TMSOTf to form supercationic species with organic substrates results in it’s utilization in a wide range of synthetic applications. [3]

TMSOTf, [4] is prepared by the gradual addition of chloro­trimethylsilane to trifluoromethanesulfonic acid with stirring and protection from moisture. The mixture is heated until hydrogen chloride evolution ceases and then the product is isolated by fractional distillation. TMSOTf is also commercially available.

    References

  • 1 Noyori R. Murata S. Suzuki M. Tetrahedron  1981,  37:  3899 
  • 2 Hergott HH. Simchen G. Liebigs Ann. Chem.  1980,  1781 
  • 3 Emede H. Domsch D. Feger H. Frick U. Götz A. Hergott HH. Hofmann K. Kober W. Krägeloh K. Oesterle T. Steppan W. West W. Simchen G. Synthesis  1982, 
  • 4 Vorbrüggen H. Krolikiewicz K. Bennua D. Chem. Ber.  1981,  114:  1234 
  • 5 Emde H. Götz A. Hofmann K. Simchen G. Liebigs Ann. Chem.  1981,  1643 
  • 6 Knapp S. Gibson FS. In Org. Synth., Vol. 9   Wiley; New York: 1999. 
  • 7 Emde H. Simchen G. Synthesis  1981,  30 
  • 8 Nishizawa M. Yamamoto H. Seo K. Imagawa H. Sugihara T. Org. Lett.  2002,  4:  1947 
  • 9 Murata S. Suzuki M. Noyori R. Tetrahedron  1988,  44:  4259 
  • 10 Murata S. Suzuki M. Noyori R. J. Am. Chem. Soc.  1979,  101:  2738 
  • 11 Gassman PG. Burns SJ. Pfister KB. J. Org. Chem.  1993,  58:  1449