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Synthesis 2010(9): 1500-1504  
DOI: 10.1055/s-0029-1218688
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Mediated Homocoupling of Vinyl Dibromides to Symmetrical Diynes

Alexis Coste, François Couty, Gwilherm Evano*
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint Quentin en Yvelines, 45 avenue des Etats-Unis, 78035 Versailles Cedex, France
Fax: +33(1)39254452; e-Mail: evano@chimie.uvsq.fr;
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Publikationsverlauf

Received 7 December 2009
Publikationsdatum:
24. Februar 2010 (online)

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Abstract

1,1-Dibromoalk-1-enes were dimerized readily in the presence of copper iodide, a diamine ligand, and cesium carbonate in DMF to give symmetrical 1,3-diynes. The reaction was found to be selective and rather general, furnishing the corresponding diynes in good yields, even with complex and sensitive dibromides, and provides useful insights into the reactivity of 1,1-dibromoalk-1-enes with copper(I).

Key words

dibromoalkenes - copper catalysis - 1,3-diynes

    References

  • 1 Ramirez F. Desal NB. McKelvie N. J. Am. Chem. Soc.  1962,  84:  1745 
    CrossrefSuche in Google Scholar
  • 2a Fang Y.-Q. Lifchits O. Lautens M. Synlett  2008,  413 
  • 2b Bryan C. Aurregi V. Lautens M. Org. Synth.  2009,  86:  36 
    Suche in Google Scholar
  • 3 Corey EJ. Fuchs PL. Tetrahedron Lett.  1972,  3769 
    Crossref
  • 4a Roush WR. Moriarty KJ. Brown BB. Tetrahedron Lett.  1990,  31:  6509 
    Suche in Google Scholar
  • 4b Shen W. Synlett  2000,  737 
  • 4c Evans DA. Starr JT. J. Am. Chem. Soc.  2003,  125:  13531 
    Suche in Google Scholar
  • 4d Reed MA. Chang MT. Snieckus V. Org. Lett.  2004,  6:  2297 
    Suche in Google Scholar
  • 4e Molander GA. Yokoyama Y. J. Org. Chem.  2006,  71:  2493 
    Suche in Google Scholar
  • 5a Wang L. Shen W. Tetrahedron Lett.  1998,  39:  7625 
    Suche in Google Scholar
  • 5b Shen W. Wang L. J. Org. Chem.  1999,  64:  8873 
    Suche in Google Scholar
  • 6 Minato A. Suzuki K. Tamao K. J. Am. Chem. Soc.  1987,  109:  1257 
    CrossrefSuche in Google Scholar
  • 7a Minato A. J. Org. Chem.  1991,  56:  4052 
    Suche in Google Scholar
  • 7b Zeng X. Qian M. Hu Q. Negishi E. Angew. Chem. Int. Ed.  2004,  43:  2259 
    Suche in Google Scholar
  • 8a Soderquist JA. Leon G. Colberg JC. Martinez I. Tetrahedron Lett.  1995,  36:  3119 
    Suche in Google Scholar
  • 8b Thielges S. Meddah E. Bisseret P. Eustache J. Tetrahedron Lett.  2004,  45:  907 
    Suche in Google Scholar
  • 8c Fang Y.-Q. Lautens M. Org. Lett.  2005,  7:  3549 
    Suche in Google Scholar
  • 8d Fayol A. Fang Y.-Q. Lautens M. Org. Lett.  2006,  8:  4203 
    Suche in Google Scholar
  • 8e Nagamochi M. Fang Y.-Q. Lautens M. Org. Lett.  2007,  9:  2955 
    Suche in Google Scholar
  • 8f Yuen J. Fang Y.-Q. Lautens M.
    J. Org. Chem.  2007,  71:  5152 
    Suche in Google Scholar
  • 8g Fang Y.-Q. Karisch R. Lautens M. J. Org. Chem.  2007,  72:  1341 
    Suche in Google Scholar
  • 8h Fang Y.-Q. Lautens M. J. Org. Chem.  2008,  73:  538 
    Suche in Google Scholar
  • 8i Chai DI. Lautens M. J. Org. Chem.  2009,  74:  3054 
    Suche in Google Scholar
  • 8j Bryan CS. Braunger JA. Lautens M. Angew. Chem. Int. Ed.  2009,  48:  7064 
    Suche in Google Scholar
  • 9 Ma S. Xu B. Ni B. J. Org. Chem.  2000,  65:  8532 
    CrossrefPubMedSuche in Google Scholar
  • 10a Zapata AJ. Rúiz J. J. Organomet. Chem.  1994,  479:  C6 
    Suche in Google Scholar
  • 10b Shen W. Thomas SA. Org. Lett.  2000,  2:  2857 
    Suche in Google Scholar
  • 10c Lera M. Hayes CJ. Org. Lett.  2000,  2:  3873 
    Suche in Google Scholar
  • 11 Yuen J. Fang Y.-Q. Lautens M. Org. Lett.  2006,  8:  653 
    CrossrefSuche in Google Scholar
  • 12a Toumi M. Couty F. Evano G. Angew. Chem. Int. Ed.  2007,  46:  572 
    Suche in Google Scholar
  • 12b Toumi M. Couty F. Evano G. J. Org. Chem.  2007,  72:  9003 
    Suche in Google Scholar
  • 12c Toumi M. Couty F. Evano G. Synlett  2008,  29 
  • 12d Coste A. Toumi M. Wright K. Razafimahaléo V. Couty F. Marrot J. Evano G. Org. Lett.  2008,  10:  3841 
    Suche in Google Scholar
  • 12e Toumi M. Rincheval V. Young A. Gergeres D. Turos E. Couty F. Mignotte B. Evano G. Eur. J. Org. Chem.  2009,  3368 
  • 12f Evano G. Toumi M. Coste A. Chem. Commun.  2009,  4166 
  • For recent reviews, see:
  • 13a Evano G. Blanchard N. Toumi M. Chem. Rev.  2008,  108:  3054 
    Suche in Google Scholar
  • 13b Monnier F. Taillefer M. Angew. Chem. Int. Ed.  2009,  48:  6954 
    Suche in Google Scholar
  • 14a Coste A. Karthikeyan G. Couty F. Evano G. Angew. Chem. Int. Ed.  2009,  48:  4381 
    Suche in Google Scholar
  • 14b Coste A. Couty F. Evano G. Org. Lett.  2009,  11:  4454 
    Suche in Google Scholar
  • 1,1-Dibromoalk-1-enes formed symmetrical diynes in two cases:
  • 15a Upon treatment with KI and CuI in HMPT at 120 ˚C: Suzuki H. Aihara M. Yamamoto H. Takamoto Y. Ogawa T. Synthesis  1988,  236 
  • 15b

    Under palladium-catalysis: see ref. 10b.

  • Representative syntheses of symmetrical 1,3-diynes:
  • 16a Liu Q. Burton DJ. Tetrahedron Lett.  1997,  38:  4371 
    Suche in Google Scholar
  • 16b Sarkar A. Okada S. Nakanishi H. Matsuda H. Helv. Chim. Acta  1999,  82:  138 
    Suche in Google Scholar
  • 16c Takai K. Kuroda T. Nakatsukasa S. Oshima K. Nazuki H. Tetrahedron Lett.  1985,  26:  5585 
    Suche in Google Scholar
  • 16d Haley MM. Bell ML. Brand SC. Kimball DB. Pak JJ. Wan WB. Tetrahedron Lett.  1997,  38:  7483 
    Suche in Google Scholar
  • 16e Nishihara Y. Ikegashira K. Hirabayashi K. Ando J. Mori A. Hiyama T. J. Org. Chem.  2000,  65:  1780 
    Suche in Google Scholar
  • 16f Lei A. Srivastava M. Zhang X. J. Org. Chem.  2002,  67:  1969 
    Suche in Google Scholar
  • 16g 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 
    Suche in Google Scholar
  • 16h Yang F. Cui X. Li Y. Zhang J. Ren G. Wu Y. Tetrahedron  2007,  63:  1963 
    Suche in Google Scholar
  • 16i Adimurthy S. Malakar CC. Beifuss U. J. Org. Chem.  2009,  74:  5648 
    Suche in Google Scholar
  • 17 For a review, see: Siemsen P. Livingston RC. Diederich F. Angew. Chem. Int. Ed.  2000,  39:  2632 
    Suche in Google Scholar
  • For early work on copper-catalyzed transformations using combinations of CuI and 1,2-diamines as ligands, see:
  • 18a Klapars A. Huang X. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  7421 
    Suche in Google Scholar
  • 18b Jiang L. Job GE. Klapars A. Buchwald SL. Org. Lett.  2003,  5:  3667 
    Suche in Google Scholar