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Synlett 2012(1): 150-154  
DOI: 10.1055/s-0031-1290099
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Highly Effective Recyclable Palladium-Catalyzed Ligand-Free Heck Reactions under Aerobic Conditions

Peng Sun, Xiaoming Qu, Tingyi Li, Yan Zhu, Hailong Yang, Zeyong Xing, Jincheng Mao*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. of China
Fax: +86(512)65880403; e-Mail: jcmao@suda.edu.cn;
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Publication History

Received 3 September 2011
Publication Date:
09 December 2011 (online)

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Abstract

An effective protocol was developed for the Heck coupling reactions between various aryl halides and olefins. In the presence of 2 mol% of Pd(OAc)2, the desired products could be obtained in good yields under ligand-free and aerobic conditions. The catalytic system could be easily recycled for five times with high efficiency.

Key words

coupling reactions - Heck reaction - aryl halides - olefins - ligand-free

    References and Notes

  • 1a Mizoroki T. Mori K. Ozaki A. Bull. Chem. Soc. Jpn.  1971,  44:  581 
    Google Scholar
  • 1b Dieck HA. Heck RF. J. Am. Chem. Soc.  1974,  96:  1133 
    Google Scholar
  • 1c Dieck HA. Heck RF. J. Org. Chem.  1975,  40:  1083 
    Google Scholar
  • For examples, see
  • 2a Gaudin J.-M. Tetrahedron Lett.  1991,  32:  6113 
    Google Scholar
  • 2b Overman LE. Ricca DJ. Tran VD. J. Am. Chem. Soc.  1993,  115:  2042 
    Google Scholar
  • 2c Tietze LF. Buhr W. Angew. Chem., Int. Ed. Engl.  1995,  34:  1366 
    Google Scholar
  • 2d Bader RR. Baumeister P. Blaser HU. Chimia  1996,  50:  99 
    Google Scholar
  • 2e Wu TC. inventors; US  5536870. 
    Google Scholar
  • 2f Eisenstadt A. In Catalysis of Organic Reactions   Herkes FE. Marcel Dekker; New York: 1998. 
    Google Scholar
  • 3a de Meijere A. Meyer FE. Angew. Chem., Int. Ed. Engl.  1995,  33:  2379 
    Google Scholar
  • 3b Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 
    Google Scholar
  • 3c Donnay AB. Overman LE. Chem. Rev.  2003,  103:  2945 
    Google Scholar
  • 3d Whitcombe NJ. Hii KK. Gibson SE. Tetradedron  2001,  57:  7449 
    Google Scholar
  • 4 Xie G. Chellan P. Mao J. Chibale K. Smith GS. Adv. Synth. Catal.  2010,  352:  1641 
    Google Scholar
  • 5 Farina V. Adv. Synth. Catal.  2004,  346:  1553 
    Google Scholar
  • 6a Carrow BP. Hartwig JF. J. Am. Chem. Soc.  2010,  132:  79 
    Google Scholar
  • 6b Reetz MT. de Vries JG. Chem. Commun.  2004,  1559 
    Google Scholar
  • 6c Zhang Z. Zha Z. Gan C. Pan C. Zhou Y. Wang Z. Zhou M.-M. J. Org. Chem.  2006,  71:  4339 
    Google Scholar
  • 7a Zhang Z. Wang Z. J. Org. Chem.  2006,  71:  7485 
    Google Scholar
  • 7b Li S. Lin Y. Xie H. Zhang S. Xu J. Org. Lett.  2006,  8:  391 
    Google Scholar
  • 7c Niembro S. Shafir A. Vallribera A. Alibés R. Org. Lett.  2008,  10:  3215 
    Google Scholar
  • 7d Bernini R. Cacchi S. Fabrizi G. Forte G. Niembro S. Petrucci F. Pleixats R. Prastaro A. Sebastián RM. Soler R. Tristany M. Vallribera A. Org. Lett.  2008,  10:  561 
    Google Scholar
  • 7e Srivastava R. Venkatathri N. Srinivas D. Ratnasamy P. Tetrahedron Lett.  2003,  44:  3649 
    Google Scholar
  • 8 Poly(ethylene glycol): Chemistry and Biological Applications   Harris JM. Zalipsky S. American Chemical Society; Washington DC: 1997. 
    Google Scholar
  • 10a Beller M. Riermeier TH. Eur. J. Inorg. Chem.  1998,  29 
    Google Scholar
  • 10b Caló V. Nacci A. Monopoli A. Detomaso A. Italiade P. Organometallics  2003,  22:  4193 
    Google Scholar
  • 10c Nadri S. Joshiaghani M. Rafiee E. Tetrahedron Lett.  2009,  50:  5470 
    Google Scholar
  • 11a Han W. Liu C. Jin Z.-L. Org. Lett.  2007,  9:  4005 
    Google Scholar
  • 11b Han W. Liu C. Jin Z.-L. Adv. Synth. Catal.  2008,  350:  2477 
    Google Scholar
  • 11c Luo C. Zhang Y. Wang Y. J. Mol. Catal. A: Chem.  2005,  229:  7 
    Google Scholar
  • 11d Du Z. Zhou W. Bai L. Wang F. Wang J.-X. Synlett  2011,  369 
    Google Scholar
  • 11e Han W. Liu N. Liu C. Jin ZL. Chin. Chem. Lett.  2010,  21:  1411 
    Google Scholar
9

General Procedure for the Ligand-Free Palladium-Catalyzed Heck-Type Coupling Reactions of Aryl Halide and Terminal Olefin
A mixture of aryl halide (0.5 mmol), olefin (3.0 mmol), Pd(OAc)2 (2 mol%), K2CO3 (2 equiv), and TBAF (2 g) in a sealed tube was stirred under air atmosphere at 70 ˚C for the desired time until complete consumption of starting material as monitored by TLC. After the mixture was poured into Et2O, then the mixture was washed with H2O, extracted with EtOAc, dried over anhyd Na2SO4, filtered and evaporated under vacuum, and the residue was purified by flash column chromatography (PE or PE-EtOAc) to afford the corresponding coupling products.
( E )-Methyl Cinnamate
¹H NMR (400 MHz, CDCl3): δ = 3.82 (s, 3 H), 6.45 (d, J = 16.0 Hz, 1 H), 7.39 (t, J = 3.2 Hz, 3 H), 7.52-7.55 (m, 2 H), 7.71 (d, J = 16.0 Hz, 1 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 52.1, 118.0, 128.4, 129.2, 130.6, 134.6, 145.2, 167.8 ppm. HRMS (ESI+): m/z calcd for [C10H10O2]+: 162.0681; found: 162.0679.