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Synthesis 2005(12): 2055-2060  
DOI: 10.1055/s-2005-870017
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart · New York

Diallene Formation by Copper(I)-Mediated Reactions of Zirconacyclo­pentanes with Propargyl Halides

Zheng Duana,b, Takahiro Nishimotoa,b, Masamichi Ogasawaraa,b, Tamotsu Takahashi*a,b
a Catalysis Research Center and Graduate School of Pharmaceutical Sciences, Hokkaido University, Kita-ku, Sapporo 001-0021, Japan
b SORST, Japan Science and Technology Agency (JST), Kita-ku, Sapporo 001-0021, Japan
Fax: +81(11)7069150; e-Mail: tamotsu@cat.hokudai.ac.jp;
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Publication History

Received 14 February 2005
Publication Date:
07 July 2005 (online)

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Abstract

In the presence of CuCl, zirconacyclopentanes reacted with two equivalents of a propargyl halide to give bisallenylation products in moderate to high yields. By controlling the amount of CuCl, stepwise allenylation was achieved and a variety of unsymmetrically substituted diallene derivatives were prepared as well.

Key words

propargyl electrophile - zirconacyclopentane - allene - SN2′ reaction - copper(I) chloride

    References

  • 1 Takahashi T. Kotora M. Kasai K. Suzuki N. Organometallics  1994,  13:  4183 
    CrossrefSearch in Google Scholar
  • 2 Kotora M. Noguchi Y. Takahashi T. Collect. Czech. Chem. Commun.  1999,  64:  1119 
    CrossrefSearch in Google Scholar
  • For copper-mediated C-C bond formation, see:
  • 3a Takahashi T. Kotora M. Xi Z. J. Chem. Soc., Chem. Commun.  1995,  1503 
    Crossref
  • 3b Takahashi T. Nishihara Y. Hara R. Huo S. Kotora M. Chem. Commun.  1997,  1599 
    Crossref
  • 3c Liu Y. Xi C. Hara R. Nakajima K. Yamazaki A. Kotora M. Takahashi T. J. Org. Chem.  2000,  65:  6951 
    CrossrefSearch in Google Scholar
  • 3d Lipshutz BH. Ellsworth E. J. Am. Chem. Soc.  1990,  112:  7440 
    CrossrefSearch in Google Scholar
  • 3e Babiak KA. Behling JR. Dygos JH. McLanghlin KT. Ng JS. Kalish VJ. Kramer SW. Shone RL. J. Am. Chem. Soc.  1990,  112:  7441 
    CrossrefSearch in Google Scholar
  • 3f Lipshutz BH. Hato K. Tetrahedron Lett.  1991,  32:  5647 
    CrossrefSearch in Google Scholar
  • 3g Lipshutz BH. Fatheree P. Hagan W. Stevens KL. Tetrahedron Lett.  1992,  33:  1041 
    CrossrefSearch in Google Scholar
  • 3h Lipshutz BH. Keil R. J. Am. Chem. Soc.  1992,  114:  7919 
    CrossrefSearch in Google Scholar
  • 3i Lipshutz BH. Wood MR. J. Am. Chem. Soc.  1993,  115:  12625 
    CrossrefSearch in Google Scholar
  • For transmetallation of alkylzirconocene to copper, see:
  • 4a Wipf P. Smitrovich JH. J. Org. Chem.  1991,  56:  6494 
    CrossrefSearch in Google Scholar
  • 4b Venanzi LM. Lehmann R. Keil R. Lipshutz BH. Tetrahedron Lett.  1992,  33:  5857 
    CrossrefSearch in Google Scholar
  • 4c Wipf P. Smitrovich JH. Moon C.-W. J. Org. Chem.  1992,  57:  3178 
    CrossrefSearch in Google Scholar
  • 4d Wipf P. Xu WJ. Smitrovich JH. Lehmann R. Venanzi LM. Tetrahedron  1994,  50:  1935 
    CrossrefSearch in Google Scholar
  • 4e Kasai K. Kotora M. Suzuki N. Takahashi T. J. Chem. Soc., Chem. Commun.  1995,  109 
    Crossref
  • SN2′ substitutions on propargyl electrophiles giving allenes have been well-established. However, in many cases, it has been encountered selectivity problems between the SN2′ and SN2 pathways, see:
  • 5a Hopf H. In The Chemistry of Ketenes, Allenes, and Related Compounds   Patai S. Wiley-Interscience; Chichester: 1980.  p.783 
  • 5b Landor PD. In The Chemistry of the Allenes   Landor SR. Academic Press; London: 1982.  p.19 
  • 5c Sandler SR. Karo W. Organic Functional Group Preparations   Vol. II, 2nd Ed.:  Academic Press; London: 1986.  p.13 
    Search in Google Scholar
  • 5d Brandsma L. Synthesis of Acetylenes, Allenes and Cumulenes: Methods and Techniques   Elsevier; Amsterdam: 2004.  p.235 
  • 5e Hoffmann-Röder A. Krause N. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.51 
  • For preparation and reactions of bisallenic compounds, see:
  • 6a Hopf H. In The Chemistry of Ketenes, Allenes, and Related Compounds   Patai S. Wiley-Interscience; Chichester: 1980.  p.799 
  • 6b Landor PD. In The Chemistry of the Allenes   Landor SR. Academic Press; London: 1982.  p.223 
  • 6c Schuster HF. Coppola GM. Allenes in Organic Synthesis   Wiley-Interscience; New York: 1984.  p.125 
  • 6d Hopf H. In Modern Allene Chemistry   Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.199 
  • 7a Negishi E. Cederbaum FE. Takahashi T. Tetrahedron Lett.  1986,  27:  2829 
    CrossrefSearch in Google Scholar
  • 7b Negishi E. Holms SJ. Tour JM. Miller JA. Cederbaum FE. Swanson DR. Takahashi T. J. Am. Chem. Soc.  1989,  111:  3336 
    CrossrefSearch in Google Scholar
  • 8a Rousset CJ. Swanson DR. Lamaty F. Negishi E. Tetrahedron Lett.  1989,  30:  5105 
    CrossrefSearch in Google Scholar
  • 8b Nugent WA. Taber DF. J. Am. Chem. Soc.  1989,  111:  6435 
    CrossrefSearch in Google Scholar
  • 9a Negishi E. Rousset CJ. Choueiry D. Maye JP. Suzuki N. Takahashi T. Inorg. Chim. Acta  1998,  280:  8 
    CrossrefSearch in Google Scholar
  • 9b Mirza-Aghayan M. Boukherroub R. Oba G. Manuel G. Koenig M. J. Organomet. Chem.  1998,  564:  61 
    CrossrefSearch in Google Scholar
  • 9c Liu Y. Shen B. Kotora M. Takahashi T. Angew. Chem. Int. Ed.  1999,  38:  949 
    CrossrefSearch in Google Scholar
  • 10 Akita M. Yasuda H. Yamamoto H. Nakamura A. Polyhedron  1991,  10:  1 
    CrossrefSearch in Google Scholar