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Synthesis 2004(6): 905-908  
DOI: 10.1055/s-2004-816008
PAPER
© Georg Thieme Verlag Stuttgart · New York

Practical Synthesis of Chlorosilyl-Functionalized Triphenylphosphanes

Delphine Quintard, Manfred Keller, Bernhard Breit*
Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104 Freiburg, Germany
Fax: +49(761)2038715; e-Mail: bernhard.breit@organik.chemie.uni-freiburg.de;
Further Information

Publication History

Received 29 January 2004
Publication Date:
15 March 2004 (online)

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Abstract

A practical synthesis of ortho-dialkylchlorosilyl-functionalized triarylphosphanes has been developed. An X-ray crystal structure analysis of phosphane 3 unambiguously confirmed the constitution of the new phosphane functionalized chlorosilanes. It also showed an interesting P/Si interaction, which may render this compound a model for the early stages of the mechanism of SN2 nucleophilic displacement at silicon.

Key words

phosphorus - silicon - ligands

    References

  • 1a Collman JP. Hegedus LS. Norton JR. Finke RG. Principles and Applications of Organotransition Metal Chemistry   University Science Books; Mill Valley: 1987.  Chap. 3.3. p.66 
    Google Scholar
  • 1b Applied Homogeneous Catalysis with Organometallic Compounds   Vol. 1:  Cornils B. Hermann WA. VCH; Weinheim: 1996. 
    Google Scholar
  • 1c Comprehensive Asymmetric Catalysis   Vol. 1:  Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999. 
    Google Scholar
  • 2a Bestmann HJ. Zimmermann R. In Comprehensive Organic Synthesis   Vol. 6:  Trost BM. Fleming I. Winterfeldt E. Pergamon; Oxford: 1991.  p.171 
    CrossrefGoogle Scholar
  • 2b Johnson AW. Ylides and Imines of Phosphorus   Wiley; New York: 1993. 
    CrossrefGoogle Scholar
  • 2c Maryanoff BE. Reitz AB. Chem. Rev.  1989,  89:  863 
    CrossrefGoogle Scholar
  • 3 Mukaiyama T. Angew. Chem., Int. Ed. Engl.  1975,  14:  801 ; Angew. Chem. 1976, 88, 111
    CrossrefGoogle Scholar
  • 4 Hughes DL. Org. React.  1992,  42:  335 
    Google Scholar
  • 5a Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2001,  40:  3726 ; Angew. Chem. 2001, 113, 3841
    CrossrefGoogle Scholar
  • 5b Su W. McLeod D. Verkade J. J. Org. Chem.  2003,  68:  9499 
    CrossrefGoogle Scholar
  • 5c Wang L.-C. Luis AL. Agapiou K. Krische MJ. J. Am. Chem. Soc.  2002,  124:  2402 
    CrossrefGoogle Scholar
  • 6a Trost BM. Lee C. Asymmetric Allylic Alkylation Reactions, In Catalytic Asymmetric Synthesis   2nd ed.:  Wiley-VCH; New York: 2000.  Chap. 8E. p.593 
    CrossrefGoogle Scholar
  • 6b Degrado SJ. Mizutani H. Hoveyda AH. J. Am. Chem. Soc.  2001,  123:  755 
    CrossrefGoogle Scholar
  • 7a Bertozzi CR. Science  2000,  287:  2007 
    CrossrefGoogle Scholar
  • 7b Hang HC. Yu C. Pratt MR. Bertozzi CR. J. Am. Chem. Soc.  2004,  126:  6 
    CrossrefGoogle Scholar
  • 7c Merkx R. Rijkers DTS. Kemmink J. Liskamp RMJ. Tetrahedron Lett.  2003,  44:  4515 
    CrossrefGoogle Scholar
  • 8a Breit B. Acc. Chem. Res.  2003,  36:  264 
    CrossrefPubMedGoogle Scholar
  • 8b Breit B. In Organic Synthesis Highlights V   Schmalz H.-G. Wirth T. Wiley-VCH; Weinheim: 2003.  p.68 
    CrossrefPubMedGoogle Scholar
  • 9 Harder S. Brandsma L. Kanters JA. Duisenberg A. van Lenthe JH. J. Organomet. Chem.  1991,  420:  143 
    CrossrefGoogle Scholar
  • 10 Kaftory M. Kapon M. Botoshansky M. In The Chemistry of Organic Silicon Compounds   Vol. 2:  Rappoport R. Apeloig Y. Wiley; Chichester: 1998.  Chap. 5. p.181 
    Google Scholar
  • 11a Macharashvili AA. Shklover VE. Struchkov YT. Oleneva GI. Kramarova EP. Shipov AG. Baukov YI. J. Chem. Soc., Chem. Commun.  1988,  683 
    CrossrefGoogle Scholar
  • 11b For a review, see: Bassindale AR. Glynn SJ. Taylor PG. In The Chemistry of Organic Silicon Compounds   Vol. 2:  Rappoport R. Apeloig Y. Wiley; Chichester: 1998.  Chap. 9. p.495 
    CrossrefGoogle Scholar
  • 12 Verkade JG. Quin LD. Phosphorus-31 NMR Spectrospcopy in Stereochemical Analysis   VCH Publishers; Deerfield Beach, Florida: 1987.  p.396 
    Google Scholar
13

Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-229247. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK [Fax: +44(1223)336033; E-Mail: deposit@ccdc.cam.ac.uk].