Download PDF
Synlett 2011(19): 2844-2848  
DOI: 10.1055/s-0031-1289861
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Double Arylation of Diynes and Alkynylation of Functionalized Heteroaryl Halides by a Practical Heck Reaction in an Ionic Liquid

Samer Saleh, Michel Picquet, Philippe Meunier, Jean-Cyrille Hierso*
Université de Bourgogne, Institut de Chimie Moléculaire de l’Université de Bourgogne UMR-CNRS 5260, 9 avenue Alain Savary, 21078 Dijon, France
Fax: +33(0)380393682; e-Mail: jean-cyrille.hierso@u-bourgogne.fr;
Further Information

Publication History

Received 14 July 2011
Publication Date:
09 November 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

The efficient palladium-catalyzed alkynylation of electron-rich bromoheteroarenes, incorporating deactivating electron-donating methyl and methoxy groups, and the (hetero)arylation of diynes, take place in the imidazolium ionic liquid [BMIM][BF4], as a highly polar non-volatile solvent. This method may constitute a sustainable alternative to classical solvents such as dioxane, DMF, NMP, or DMAc. New enynes are formed in the presence of a system encompassing a copper-free palladium catalyst, triphenylphosphine as ligand, and various inexpensive bases. The enyne molecules reported are selectively synthesized in high yields and are mostly unprecedented.

Key words

arylation - diynes - heteroarenes - palladium - ionic liquid

    References and Notes

  • 1a Doucet H. Hierso J.-C. Angew. Chem. Int. Ed.  2007,  46:  834 
    Google Scholar
  • 1b Negishi E.-I. Anastasia L. Chem. Rev.  2003,  103:  1979 
    Google Scholar
  • 1c Tykwinski RR. Angew. Chem. Int. Ed.  2003,  42:  1566 
    Google Scholar
  • 2a Feuerstein M. Doucet H. Santelli M. Tetrahedron Lett.  2005,  46:  1717 
    Google Scholar
  • 2b Feuerstein M. Doucet H. Santelli M. J. Mol. Catal. A: Chem.  2006,  256:  75 
    Google Scholar
  • 2c Yang F. Cui X. Li Y.-N. Ren G.-R. Wu Y. Tetrahedron Lett.  2007,  46:  1717 
    Google Scholar
  • 2d Fleckenstein CA. Plenio H. Green Chem.  2008,  10:  563 
    Google Scholar
  • 2e Mehta VP. Sharma A. Van der Eycken E. Org. Lett.  2008,  6:  1147 
    Google Scholar
  • 2f Wu M. Mao J. Guo J. Ji S. Eur. J. Org. Chem.  2008,  4050 
    Google Scholar
  • 2g Torborg C. Zapf A. Beller M. ChemSusChem  2008,  1:  91 
    Google Scholar
  • 2h Torborg C. Huang J. Schulz T. Schäffner B. Zapf A. Spannenberg A. Börner A. Beller M. Chem. Eur. J.  2009,  15:  1329 
    Google Scholar
  • 3 Dieck HA. Heck FR. J. Organomet. Chem.  1975,  93:  259 
    Google Scholar
  • 4 Sonogashira K. J. Organomet. Chem.  2002,  653:  46 
    Google Scholar
  • 5a Nakamura K. Okubo H. Yamaguchi M. Synlett  1999,  549 
    Google Scholar
  • 5b Mery D. Heuze K. Astruc D. Chem. Commun.  2003,  1934 
    Google Scholar
  • 5c Hundertmark T. Littke AF. Buchwald SL. Fu GC. Org. Lett.  2000,  2:  1729 
    Google Scholar
  • 6a Thorand S. Krause N. J. Org. Chem.  1998,  63:  8551 
    Google Scholar
  • 6b Alonso DA. Najera C. Pacheco MC. Tetrahedron Lett.  2002,  43:  9365 
    Google Scholar
  • 7a Hierso J.-C. Fihri A. Amardeil R. Meunier P. Doucet H. Santelli M. Ivanov VV. Org. Lett.  2004,  6:  3473 
    Google Scholar
  • 7b Feuerstein M. Berthiol F. Doucet H. Santelli M. Org. Biomol. Chem.  2003,  1:  2235 
    Google Scholar
  • 8a Kollhofer A. Pullmann T. Plenio H. Angew. Chem. Int. Ed.  2003,  42:  1056 
    Google Scholar
  • 8b Gelman D. Buchwald SL. Angew. Chem. Int. Ed.  2003,  42:  5993 
    Google Scholar
  • 9 Fukuyama T. Shinmen M. Nishitani S. Sato M. Ryu I. Org. Lett.  2002,  4:  1691 
    Google Scholar
  • 10 Park SB. Alper H. Chem. Commun.  2004,  1306 
    Google Scholar
  • 11a Gholap AR. Venkatesan K. Pasricha R. Daniel T. Lahoti RJ. Srinivasan KV. J. Org. Chem.  2005,  70:  4869 
    Google Scholar
  • 11b Corma A. Garcia H. Leyva A. Tetrahedron  2005,  61:  9848 
    Google Scholar
  • 11c Hierso J.-C. Picquet M. Cattey H. Meunier P. Synlett  2006,  3005 
    Google Scholar
  • 11d Hierso J.-C. Boudon J. Picquet M. Meunier P. Eur. J. Org. Chem.  2007,  583 
    Google Scholar
  • 11e Saleh S. Fayad E. Azouri M. Hierso J.-C. Andrieu J. Picquet M. Adv. Synth. Catal.  2009,  351:  1621 
    Google Scholar
  • 11f Saleh S. Picquet M. Meunier P. Hierso J.-C. Tetrahedron  2009,  65:  7146 
    Google Scholar
  • 12a Welton T. Chem. Rev.  1999,  99:  2071 
    Google Scholar
  • 12b Dupont J. de Souza RF. Suarez PAZ. Chem. Rev.  2002,  102:  3667 
    Google Scholar
  • 12c Wasserscheid P. Keim W. Angew. Chem. Int. Ed.  2000,  39:  3772 
    Google Scholar
  • 12d Sheldon R. Chem. Commun.  2001,  2399 
    Google Scholar
  • 12e Dyson PJ. Transition Met. Chem.  2002,  27:  353 
    Google Scholar
  • 12f Olivier-Bourbigou H. Magna L. J. Mol. Catal. A: Chem.  2002,  182:  419 
    Google Scholar
  • 12g Picquet M. Poinsot D. Stutzmann S. Tkatchenko I. Tommasi I. Wasserscheid P. Zimmermann J. Top. Catal.  2004,  29:  139 
    Google Scholar
  • 13a Zhang Z. Lockman PR. Mittapalli RK. Allen DD. Dwoskin LP. Crooks PA. Bioorg. Med. Chem. Lett.  2008,  18:  5622 
    Google Scholar
  • 13b Hay C. Hissler M. Fischmeister C. Rault-Berthelot J. Toupet L. Nyulàszi L. Réau R. Chem. Eur. J.  2001,  7:  4222 
    Google Scholar
  • 14 Cacchi S. Fabrizi G. Chem. Rev.  2011,  111:  215 
    Google Scholar
15

Typical procedure: The catalyst was prepared as a solid mixture of [Pd(allyl)Cl]2 (6.3 mg, 0.034 mmol of Pd) and Ph3P (26.9 mg, 0.102 mmol), and degassed for 15 min in a 20 mL Schlenk tube equipped with a magnetic stirrer bar and a reflux condenser. Under argon, were added the heteroaryl halide (either solid or liquid, 3.42 mmol) and [BMIM][BF4] (3 mL). The mixture was further degassed under reduced pressure for 10 min. The Schlenk tube was heated in an oil bath at 60 ˚C to give a red solution. The vessel was removed from the heating bath and, to the ionic liquid solution, was then added pyrrolidine (0.35 mL, 292 mg, 4.1 mmol) and the terminal alkyne (4.1 mmol). The resulting mixture was heated at 100 ˚C for 4 h under argon and, after extraction with diethyl ether (4 × 5 mL), the product was purified by silica gel chromatography (ethyl acetate-heptane, 1:9) to give the enyne compound. The recovered ionic liquid can be reused without treatment for further catalytic couplings, after removal of ether traces by simple evaporation under vacuum. Reloading of triphenylphosphine may be necessary after three runs due to a partial organic extraction, no amine salt removal was done during this recycling.

16

Copies of ¹H and ¹³C NMR spectra of products 1-22 and detailed assignment are reported as Supporting Information.