Download PDF
Synlett 2002(9): 1529-1531
DOI: 10.1055/s-2002-33535
LETTER
© Georg Thieme Verlag Stuttgart · New York

Efficient Pd(0)-Catalyzed Hydrosilylation of Alkynes with Triorganosilanes

Dai Motoda, Hiroshi Shinokubo, Koichiro Oshima*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
Fax: +81(75)7534863; e-Mail: oshima@fm1.kuic.kyoto-u.ac.jp;
Further Information

Publication History

Received 20 May 2002
Publication Date:
17 September 2002 (online)

    Permissions and Reprints All articles of this category

Abstract

An electron-rich Pd(0) complex, a Pd2(dba)3·CHCl3-tricyclohexylphosphine combination catalyzes highly efficient hydrosilylation of alkynes at room temperature with Ph3SiH or Ph2MeSiH without solvents. The regioselectivity of this process is higher than that with the conventional Pt(0)-catalyzed hydrosilyl­ation.

Key words

hydrosilylation - palladium - phosphine - alkyne - alkene

    References

  • 1a Hiyama T. Kusumoto T. In Comprehensive Organic Synthesis   Vol. 8:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  Chap. 3.12.
    Google Scholar
  • 1b Ojima I. Li Z. Zhu J. In The Chemistry of Organosilicon Compounds, Part 2   Vol. 2:  Rappoport Z. Apeloig Y. Wiley; Chichester: 1998.  Chap. 29.
    Google Scholar
  • 1c Corey JY. In Advances in Silicon Chemistry   Larson GL. JAI; Greenwich: 1991.  p.355 
    Google Scholar
  • 1d Marciniec B. Comprehensive Handbook on Hydrosilylation   Pergamon Press; Oxford: 1992. 
    Google Scholar
  • 2 Recent examples of hydrosilylation with other catalysts. Ni catalysis: Maciejewski H. Marciniec B. Kownacki I. J. Organomet. Chem.  2000,  597:  175 
    CrossrefGoogle Scholar
  • Ru catalysis:
  • 3a Trost BM. Ball ZT. J. Am. Chem. Soc.  2001,  123:  12726 
    CrossrefGoogle Scholar
  • 3b Na Y. Chang S. Org. Lett.  2000,  2:  1887 
    CrossrefGoogle Scholar
  • 3c Katayama H. Taniguchi K. Kobayashi M. Sagawa T. Minami T. Ozawa F. J. Organomet. Chem.  2002,  645:  192 
    CrossrefGoogle Scholar
  • Lewis acid catalysis:
  • 4a Asao N. Sudo T. Yamamoto Y. J. Org. Chem.  1996,  61:  7654 
    CrossrefGoogle Scholar
  • 4b Sudo T. Asao N. Gevorgyan V. Yamamoto Y. J. Org. Chem.  1999,  64:  2494 
    CrossrefGoogle Scholar
  • 4c Yamamoto K. Takemae M. Synlett  1990,  259 
    CrossrefGoogle Scholar
  • 4d Rubin M. Schwier T. Gevorgyan N. J. Org. Chem.  2002,  67:  1936 
    CrossrefGoogle Scholar
  • 4e Song YS. Yoo BR. Lee GH. Jung IN. Organometallics  1999,  18:  3109 
    CrossrefGoogle Scholar
  • 4f Buriak JM. Allen MJ. J. Am. Chem. Soc.  1998,  120:  1339 
    CrossrefGoogle Scholar
  • Radical Catalysis:
  • 5a Miura K. Oshima K. Utimoto K. Bull. Chem. Soc. Jpn.  1993,  66:  2356 
    CrossrefGoogle Scholar
  • 5b Amrein S. Timmermann A. Studer A. Org. Lett.  2001,  3:  2357 
    CrossrefGoogle Scholar
  • 6a Ojima I. Yatabe M. Fuchikami T. J. Organomet. Chem.  1984,  260:  335 
    CrossrefGoogle Scholar
  • 6b Hydrosilylation with cationic palladium complexes has been reported, see: Winderhoefer RA. Vadera A. Cheruvu PK. Organometallics  1999,  18:  4614 
    CrossrefGoogle Scholar
  • 6c Pd-catalyzed hydrosilylation with dimerization of alkynes: Kawanami Y. Yamamoto K. Synlett  1995,  1232 
    CrossrefGoogle Scholar
  • 6d The Pd2dba3·CHCl3-Cy3P-catalyzed reaction of alkynes with PhSiH3 has been reported, see: Yamashita H. Uchimaru Y. Chem. Commun.  1999,  1763 
    CrossrefGoogle Scholar
  • 7a Jensen JF. Svendsen BY. la Cour TV. Pedersen HL. Johannsen M. J. Am. Chem. Soc.  2002,  124:  4558 
    CrossrefGoogle Scholar
  • 7b Shimada T. Mukaide K. Shinohara A. Han JW. Hayashi T. J. Am. Chem. Soc.  2002,  124:  1584 
    CrossrefGoogle Scholar
  • 7c Han JW. Tokunaga N. Hayashi T. J. Am. Chem. Soc.  2001,  123:  12915 
    CrossrefGoogle Scholar
  • 7d Hayashi T. In Comprehensive Asymmetric Catalysis   Vol. 1:  Jacobsen NE. Pfaltz A. Yamamoto H. Springer; Berlin: 1999.  Chap. 7.
    CrossrefGoogle Scholar
  • 7e Hayashi T. Acta Chem. Scand.  1996,  50:  259 
    CrossrefGoogle Scholar
  • 7f Nishiyama H. Itoh K. In Catalytic Asymmetric Synthesis   2nd ed.:  Ojima I. VCH; New York: 2000.  p.111-143  
    CrossrefGoogle Scholar
  • 8 For the use of electron rich Pd(0)/trialkylphoshine catalysts, see: Netherton MR. Fu GC. Org. Lett.  2001,  3:  4295 ; and ref. 3 therein
    CrossrefPubMedGoogle Scholar
  • 9a Lewis LN. Sy KG. Bryant GL. Donahue PE. Organometallics  1991,  10:  3750 
    CrossrefGoogle Scholar
  • 9b Lewis LN. Sy KG. Donahue PE. J. Organomet. Chem.  1992,  427:  165 
    CrossrefGoogle Scholar
  • 9c Chauhan M. Hauck BJ. Keller LP. Boudjouk P. J. Organomet. Chem.  2002,  645:  1 
    CrossrefGoogle Scholar
  • 9d For hydrosilylation with Ph3SiH under other metal catalyses, see: Bartik T. Nagy G. Kvintovics P. Happ B. J. Organomet. Chem.  1993,  453:  29 
    CrossrefGoogle Scholar
  • 9e Also see: Faller JW. D’Alliessi DP. Organometallics  2002,  21:  1743 
    CrossrefGoogle Scholar
  • 12 Kinoshita H. Nakamura T. Kakiya H. Shinokubo H. Matsubara S. Oshima K. Org. Lett.  2001,  3:  2521 
    CrossrefGoogle Scholar
10

Experimental Procedure: The reaction of dodec-1-en-11-yne with Ph3SiH is representative. In a 30 mL round-bottomed flask, Pd2(dba)3·CHCl3 (5.2 mg, 0.005 mmol) and tricyclohexylphosphine (5.6 mg, 0.02 mmol) were placed under argon atmosphere, and dodec-1-en-11-yne (0.26 mL, 1.2 mmol) was introduced via a syringe. The mixture was stirred well for 10 min to make it homogeneous. To the mixture, triphenylsilane (260 mg, 1.0 mmol) was added at room temperature. Triphenylsilane was soon dissolved and the mixture became homogeneous. After 1 h, the reaction mixture was submitted on silica gel purification to provide (E)-1-triphenylsilyl-dodeca-1,11-diene (369 mg, 0.87 mmol) in 87% yield along with a minor amount of 2-triphenylsilyl-dodeca-1,11-diene (3%).

11

None of alkenylsilanes were obtained with triethylsilane.

13

Experimental Procedure for Aqueous Reaction: In a round-bottomed flask, Pd2(dba)3·CHCl3 (5.2 mg, 0.005 mmol), tris(2,4,6-trimethoxyphenyl)phosphine (10.7 mg, 0.02 mmol), and 1-octyne (0.30 mL, 2.0 mmol) were mixed well. To the mixture, distilled water (5 mL, non-degassed) was introduced and the mixture was stirred vigorously (1500 rpm) for 5 min. Triphenylsilane (260 mg, 1.0 mmol) was then added, and the heterogeneous mixture was stirred vigorously for 6 h. Extractive workup and purification provided (E)-1-triphenylsilyl-1-octene (256 mg, 0.69 mmol) along with 2-triphenylsilyl-1-octene (13%).

14

An addition of a small amount of water (0.1 mL) to the neat reaction did not enhance the reactivity. Therefore, the amount of water is essential.