Elsevier

Tetrahedron Letters

Volume 45, Issue 1, 1 January 2004, Pages 87-90
Tetrahedron Letters

Synthesis of new silylated sulfur-containing heterocycles through thionation of bis(acylsilanes)

https://doi.org/10.1016/j.tetlet.2003.10.110Get rights and content

Abstract

The thionation of bis(acylsilanes) with spacers of variable size with hexamethyldisilathiane under cobalt(II) chloride or trimethylsilyl triflate catalysis affords 2,5-bis(trialkylsilyl)-thiophenes, 2,6-bis(trialkylsilyl)-4H-thiopyrans and 2,7-bis(trialkylsilyl)-4,5-dihydrothiepine generally along with a minor amount of the corresponding oxo analogue. The synthesis of both symmetrical and unsymmetrical bis(trialkylsilyl) derivatives was achieved.

Reaction of bis(acylsilanes), with spacers of variable size, with HMDST affords symmetrical and unsymmetrical silylated thiophene-, thiopyran- and dihydrothiepine derivatives.

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Acknowledgements

The authors gratefully acknowledge Professor Alfredo Ricci, University of Bologna, for helpful discussions.

References (13)

  • B.F. Bonini et al.

    Eur. J. Org. Chem.

    (2000)
  • A.G. Brook et al.

    J. Am. Chem. Soc.

    (1957)
    A. Ricci et al.

    Synthesis

    (1989)
    P.C.B. Page et al.

    Chem. Soc. Rev.

    (1990)
    P.F. Cirillo et al.

    Org. Prep. Proced. Int.

    (1992)
    C. Nàjera et al.

    Org. Prep. Proced. Int.

    (1995)
    B.F. Bonini et al.

    Gazz. Chim. Ital.

    (1997)
    B.F. Bonini et al.

    J. Organomet. Chem.

    (1998)
    P.C.B. Page et al.
  • A. Capperucci et al.

    J. Org. Chem.

    (1988)
    T.-H. Chuang et al.

    J. Org. Chem.

    (1996)
    J.-P. Bouillon et al.

    Eur. J. Org. Chem.

    (1999)
  • D. Saleur et al.

    Tetrahedron Lett.

    (1999)
    J.-P. Bouillon et al.

    Synthesis

    (2000)
    J.-P. Bouillon et al.

    J. Org. Chem.

    (2000)
  • D. Saleur et al.

    Synlett

    (1999)
    D. Saleur et al.

    J. Org. Chem.

    (2001)
    J.-P. Bouillon et al.

    Eur. J. Org. Chem.

    (2001)
There are more references available in the full text version of this article.

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