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Synthesis 2010(20): 3461-3466  
DOI: 10.1055/s-0030-1258199
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Copper(II) Acetate Catalyzed Homo- and Heterocoupling of Terminal Alkynes at Ambient Conditions

Kaluvu Balaraman, Venkitasamy Kesavan*
Department of Biotechnology, Indian Institute of Technology Madras, Chennai 600036, India
Fax: +91(44)22574102; e-Mail: vkesavan@iitm.ac.in;
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Publication History

Received 14 June 2010
Publication Date:
05 August 2010 (online)

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Abstract

Symmetrical 1,3-diynes were obtained in quantitative yields using the copper(II) acetate catalyzed homocoupling of terminal alkynes in the presence of a stoichiometric amount of piperidine at 25 ˚C under aerobic conditions. We also accomplished facile syntheses of unsymmetric 1,3-diynes by heterocoupling terminal alkynes in very good yields under the reported reaction conditions.

Key words

terminal alkynes - copper(II) acetate - piperidine - homocoupling - heterocoupling - symmetric 1,3-diynes - unsymmetric 1,3-diynes

    References

  • 1a Holmes AB. Jennings-White CLD. Kendrick DA. J. Chem. Soc., Chem. Commun.  1983,  415 
    Google Scholar
  • 1b Nicolaou KC. Zipkin RE. Dolle RE. Harris BD. J. Am. Chem. Soc.  1984,  106:  3548 
    Google Scholar
  • 1c Crombie L. Hobbs AJW. Horsham MA. Blade RJ. Tetrahedron Lett.  1987,  28:  4875 
    Google Scholar
  • 1d Holmes AB. Tabor AB. Baker R. J. Chem. Soc., Perkin Trans. 1  1991,  3307 
    Google Scholar
  • 1e Hoye TR. Hanson PR. Tetrahedron Lett.  1993,  34:  5043 
    Google Scholar
  • 1f Shi Shun ALK. Tykwinski RR. Angew. Chem. Int. Ed.  2006,  45:  1034 
    Google Scholar
  • 2 Stütz A. Angew. Chem. Int. Ed.  1987,  26:  320 
    CrossrefGoogle Scholar
  • 3a Bohlmann F. Burkhardt T. Zdero C. Naturally Occurring Acetylenes   Academic Press; London: 1973. 
    Google Scholar
  • 3b Hansen L. Boll PM. Phytochemistry  1986,  25:  285 
    Google Scholar
  • 3c Matsunaga H. Katano M. Yamamoto H. Fujito H. Mori M. Takata K. Chem. Pharm. Bull.  1990,  38:  3480 
    Google Scholar
  • 3d Shi Shun ALK. Tykwinski RR. Angew. Chem. Int. Ed.  2006,  45:  1034 
    Google Scholar
  • 4a Acetylene Chemistry: Chemistry, Biology and Material Science   Diederich F. Stang P. Tykwinski RR. Wiley-VCH; Weinheim: 2005. 
    Google Scholar
  • 4b Carbon-Rich Compounds: From Molecules to Materials   Haley MM. Tykwinski RR. Wiley-VCH; Weinheim: 2006. 
    Google Scholar
  • 5a Glaser C. Ber. Dtsch. Chem. Ges.  1869,  2:  422 
    Google Scholar
  • 5b Glaser C. Ann. Chem. Pharm.  1870,  154:  137 
    Google Scholar
  • 6 Eglinton G. Galbraith AR. Chem. Ind. (London)  1956,  737 
    Google Scholar
  • 7a Hay AS. J. Org. Chem.  1960,  25:  1275 
    Google Scholar
  • 7b Hay AS. J. Org. Chem.  1962,  27:  3320 
    Google Scholar
  • 8a Sonogashira K. Tohda Y. Hagihara N. Tetrahedron Lett.  1975,  16:  4467 
    Google Scholar
  • 8b Sonogashira K. Coupling Reactions between sp Carbon Centers, In Comprehensive Organic Synthesis   Vol. 3:  Trost BM. Fleming I. Pergamon; Oxford: 1990.  p.521 
    Google Scholar
  • 9 Cadiot P. Chodkiewicz W. Chemistry of Acetylenes   Viehe HG. Marcel Dekker; New York: 1969.  p.597 
    Google Scholar
  • 10a Rossi R. Carpita A. Bigelli C. Tetrahedron Lett.  1985,  26:  523 
    Google Scholar
  • 10b Vlassa M. Ciocan-Tarta I. Mãrgineanu F. Oprean I. Tetrahedron  1996,  52:  1337 
    Google Scholar
  • 10c Liu Q. Burton DJ. Tetrahedron Lett.  1997,  38:  4371 
    Google Scholar
  • 10d Lei A. Srivastava M. Zhang X. J. Org. Chem.  2002,  67:  1969 
    Google Scholar
  • 10e Fairlamb IJS. Bäuerlein PSB. Marrison LR. Dickinson JM. Chem. Commun.  2003,  632 
    Google Scholar
  • 10f Batsanov AS. Collings JC. Fairlamb IJS. Holland JP. Howard JAK. Lin Z. Marder TB. Parsons AC. Ward RM. Zhu J. J. Org. Chem.  2005,  70:  703 
    Google Scholar
  • 10g Li JH. Liang Y. Zhang XD. Tetrahedron  2005,  61:  1903 
    Google Scholar
  • 10h Li JH. Liang Y. Xie YX. J. Org. Chem.  2005,  70:  4393 
    Google Scholar
  • 10i Shi M. Qian HX. Appl. Organomet. Chem.  2006,  20:  771 
    Google Scholar
  • 10j Yan J. Wu J. Jin H. J. Organomet. Chem.  2007,  692:  3636 
    Google Scholar
  • 11 Li D. Yin K. Li J. Jia X. Tetrahedron Lett.  2008,  49:  5918 
    CrossrefGoogle Scholar
  • 12 Li L. Wang J. Zhang G. Liu Q. Tetrahedron Lett.  2009,  50:  4033 
    CrossrefGoogle Scholar
  • 13 Kuhn P. Alix A. Kumarraja M. Louis B. Pale P. Sommer J. Eur. J. Org. Chem.  2009,  423 
    CrossrefGoogle Scholar
  • 14 Adimurthy S. Malakar CC. Beifuss U. J. Org. Chem.  2009,  74:  5648 
    CrossrefGoogle Scholar
  • 15a Li J. Jiang H. Chem. Commun.  1999,  2369 
    Google Scholar
  • 15b Jiang HF. Tang JY. Wang AZ. Deng GH. Yang SR. Synthesis  2006,  1155 
    Google Scholar
  • 16 Nishihara Y. Okamoto M. Inoue Y. Miyazaki M. Miyasaka M. Takagi K. Tetrahedron Lett.  2005,  46:  8661 
    CrossrefGoogle Scholar
  • 17 Paxião MW. Weber M. Braga AL. De Azeredo JB. Deobald AB. Stefani HA. Tetrahedron Lett.  2008,  49:  2366 
    CrossrefGoogle Scholar
  • 18 Zhu BC. Jiang XZ. Appl. Organomet. Chem.  2007,  21:  345 
    CrossrefGoogle Scholar
  • 19 Kamata K. Yamaguchi S. Kotani M. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed.  2008,  47:  2407 
    CrossrefGoogle Scholar
  • 20a Alami M. Ferri F. Tetrahedron Lett.  1996,  37:  2763 
    Google Scholar
  • 20b Nishihara Y. Ikegashira K. Mori A. Hiyama T. Tetrahedron Lett.  1998,  39:  4075 
    Google Scholar
  • 20c Montierth JM. DeMario DR. Kurth MJ. Schore NE. Tetrahedron  1998,  54:  11741 
    Google Scholar
  • 20d Kim S. Kim S. Lee T. Ko H. Kim D. Org. Lett.  2004,  6:  3601 
    Google Scholar
  • 21a Miyaura N. Yamada K. Suzuki A. Tetrahedron Lett.  1979,  20:  3437 
    Google Scholar
  • 21b Wityak J. Chan JB. Synth. Commun.  1991,  21:  977 
    Google Scholar
  • 21c Amatore C. Blart E. Genet JP. Jutand A. Lemaire-Audoire S. Savignac M. J. Org. Chem.  1995,  60:  6829 
    Google Scholar
  • 22 Yin W. He C. Chen M. Zhang H. Lei A. Org. Lett.  2009,  11:  709 
    CrossrefPubMedGoogle Scholar
  • 23 Wang D. Li J. Li N. Gao T. Hou S. Chen B. Green Chem.  2010,  12:  45 
    CrossrefGoogle Scholar