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Efficient and ligand free palladium catalyst for Suzuki and Heck cross-coupling reactions

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Abstract

A simple and efficient system for Suzuki cross-coupling reactions was developed using a ligandless catalyst of Pd nanoclusters generated in situ from Pd(acac)2. The cross-coupling reactions proceeded under mild reaction conditions with a high reaction rate (5 min) to give various biaryls in high yields. The system also exhibited catalytic potential for Heck reaction between aryl bromides and styrene.

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References

  1. Shahnaz N, Banik B, Das P. A highly efficient schiff-base derived palladium catalyst for the Suzuki-Miyaura reactions of aryl chlorides. Tetrahedron Lett, 2013, 54: 2886–2889

    Article  CAS  Google Scholar 

  2. Miyaura N, Suzuki A. Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem Rev, 1995, 95: 2457–2483

    Article  CAS  Google Scholar 

  3. Littke AF, Das CY, Fu GC. Versatile catalysts for the Suzuki cross-coupling of arylboronic acids with aryl and vinyl halides and triflates under mild conditions. J Am Chem Soc, 2000, 122: 4020–4028

    Article  CAS  Google Scholar 

  4. Han W, Liu C, Jin ZL. In situ generation of palladium nanoparticles: a simple and highly active protocol for oxygen-promoted ligand-free Suzuki coupling reaction of aryl chlorides. Org Lett, 2007, 9: 4005–4007

    Article  CAS  Google Scholar 

  5. Martin R, Buchwald SL. Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions employing dialkylbiaryl phosphine ligands. Acc Chem Res, 2008, 41: 1461–1473

    Article  CAS  Google Scholar 

  6. Suzuki A. Recent advances in the cross-coupling reactions of organoboron derivatives with organic electrophiles, 1995–1998. J Organomet Chem, 1999, 576: 147–168

    Article  CAS  Google Scholar 

  7. Kotha S, Lahiri K, Kashinath D. Recent applications of the Suzuki-Miyaura cross-coupling reaction in organic synthesis. Tetrahedron, 2002, 58: 9633–9695

    Article  CAS  Google Scholar 

  8. Noël T, Buchwald SL. Cross-coupling in flow. Chem Soc Rev, 2011, 40: 5010–5029

    Article  Google Scholar 

  9. Hassan J, Sévignon M, Gozzi C, Schulz E, Lemaire M. Aryl-aryl bond formation one century after the discovery of the Ullmann reaction. Chem Rev, 2002, 102: 1359–1470

    Article  CAS  Google Scholar 

  10. Fihri A, Bouhrara M, Nekoueishahraki B, Basset JM, Polshettiwar V. Nanocatalysts for Suzuki cross-coupling reactions. Chem Soc Rev, 2011, 40: 5181–5203

    Article  CAS  Google Scholar 

  11. Ghosh R, Adarsh NN, Sarkar A. A novel, air-stable phosphine ligand for the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction of chloro arenes. J Org Chem, 2010, 75: 5320–5322

    Article  CAS  Google Scholar 

  12. Hanhan ME, Martínez-Máñez R, Ros-Lis JV. Highly effective activation of aryl chlorides for Suzuki coupling in aqueous media using a ferrocene-based Pd (II)-diimine catalyst. Tetrahedron Lett, 2012, 53: 2388–2391

    Article  CAS  Google Scholar 

  13. Grushin VV, Alper H. Transformations of chloroarenes, catalyzed by transition-metal complexes. Chem Rev, 1994, 94: 1047–1062

    Article  CAS  Google Scholar 

  14. Liu C, Ni QJ, Hu PP, Qiu JS. Oxygen-promoted PdCl2-catalyzed ligand-free Suzuki reaction in aqueous media. Org Biomol Chem, 2011, 9: 1054–1060

    Article  CAS  Google Scholar 

  15. Kostas ID, Andreadaki FJ, Kovala-Demertzi D, Prentjas C, Demertzis MA. Suzuki-Miyaura cross-coupling reaction of aryl bromides and chlorides with phenylboronic acid under aerobic conditions catalyzed by palladium complexes with thiosemicarbazone ligands. Tetrahedron Lett, 2005, 46: 1967–1970

    Article  CAS  Google Scholar 

  16. Littke AF, Fu GC. A convenient and general method for Pd-catalyzed Suzuki cross-couplings of aryl chlorides and arylboronic acids. Angew Chem, 1998, 37: 3387–3388

    Article  CAS  Google Scholar 

  17. Andreu MG, Zapf A, Beller M. Molecularly defined palladium(0) monophosphine complexes as catalysts for efficient cross-coupling of aryl chlorides and phenylboronic acid. Chem Commun, 2000, 24: 2475–2476

    Article  Google Scholar 

  18. Bedford RB, Cazin CSJ. Highly active catalysts for the Suzuki coupling of aryl chlorides. Chem Commun, 2001, 17: 1540–1541

    Article  Google Scholar 

  19. Kwong FY, Lam WH, Yeung CH, Chan KS, Chan ASC. A simple and highly efficient P, O-type ligand for Suzuki-Miyaura cross-coupling of aryl halides. Chem Commun, 2004, 17: 1922–1923

    Article  Google Scholar 

  20. To SC, Kwong FY. Highly efficient carbazolyl-derived phosphine ligands: application to sterically hindered biaryl couplings. Chem Commun, 2011, 47: 5079–5081

    Article  CAS  Google Scholar 

  21. Colacot TJ. A concise update on the applications of chiral ferrocenyl phosphines in homogeneous catalysis leading to organic synthesis. Chem Rev, 2003, 103: 3101–3118

    Article  CAS  Google Scholar 

  22. Kataoka N, Shelby Q, Stambuli JP, Hartwig JF. Air stable, sterically hindered ferrocenyl dialkylphosphines for palladium-catalyzed CC, CN, and CO bond-forming cross-couplings. J Org Chem, 2002, 67: 5553–5566

    Article  CAS  Google Scholar 

  23. Baillie C, Zhang LX, Xiao JL. Ferrocenyl monophosphine ligands: synthesis and applications in the Suzuki-Miyaura coupling of aryl chlorides. J Org Chem, 2004, 69: 7779–7782

    Article  CAS  Google Scholar 

  24. Teo SH, Weng ZQ, Andy Hor TS. 1, 1′-P/O-ferrocenyl ligands in palladium-catalyzed suzuki coupling of aryl chlorides. Organometallics, 2006, 25: 1199–1205

    Article  CAS  Google Scholar 

  25. Jensen JF, Johannsen M. New air-stable planar chiral ferrocenyl monophosphine ligands: Suzuki cross-coupling of aryl chlorides and bromides. Org Lett, 2003, 5: 3025–3028

    Article  CAS  Google Scholar 

  26. Donnelly KF, Petronilho A, Albrecht M. Application of 1,2,3-triazolylidenes as versatile NHC-type ligands: synthesis, properties, and application in catalysis and beyond. Chem Commun, 2013, 49: 1145–1159

    Article  CAS  Google Scholar 

  27. Enders D, Niemeier O, Henseler A. Organocatalysis by N-heterocyclic carbenes. Chem Rev, 2007, 107: 5606–5655

    Article  CAS  Google Scholar 

  28. Marion N, Navarro O, Mei JG, Stevens ED, Scott NM, Nolan SP. Modified (NHC) Pd(allyl)Cl (NHC = N-heterocyclic carbene) complexes for room-temperature Suzuki-Miyaura and Buchwald-Hartwig reactions. J Am Chem Soc, 2006, 128: 4101–4111

    Article  CAS  Google Scholar 

  29. Godoy F, Segarra C, Poyatos M, Peris E. Palladium catalysts with sulfonate-functionalized-NHC ligands for Suzuki-Miyaura cross-coupling reactions in water. Organometallics, 2011, 30: 684–688

    Article  CAS  Google Scholar 

  30. Du ZY, Zhou WW, Wang F, Wang, JX. In situ generation of palladium nanoparticles: ligand-free palladium catalyzed ultrafast Suzuki-Miyaura cross-coupling reaction in aqueous phase at room temperature. Tetrahedron, 2011, 67: 4914–4918

    Article  CAS  Google Scholar 

  31. Liu C, Zhang YX, Liu N, Qiu JS. A simple and efficient approach for the palladium-catalyzed ligand-free Suzuki reaction in water. Green Chem, 2012, 14: 2999–3003

    Article  CAS  Google Scholar 

  32. De Vries AHM, Mulders JMCA, Mommers JHM, Henderickx HJW, De Vries JG. Homeopathic ligand-free palladium as a catalyst in the Heck reaction. A comparison with a palladacycle. Org Lett, 2003, 5: 3285–3288

    Article  Google Scholar 

  33. Maegawa T, Kitamura Y, Sako S, Udzu T, Sakurai A, Tanaka A, Kobayashi Y, Endo K, Bora U, Kurita T, Kozaki A, Monguchi Y, Sajiki H. Heterogeneous pd/C-catalyzed ligand-free, room-temperature Suzuki-Miyaura coupling reactions in aqueous media. Chem Eur, 2007, 13: 5937–5943

    Article  CAS  Google Scholar 

  34. Liu C, Ni QJ, Bao FY, Qiu JS. A simple and efficient protocol for a palladium-catalyzed ligand-free Suzuki reaction at room temperature in aqueous DMF. Green Chem, 2011, 13: 1260–1266

    Article  CAS  Google Scholar 

  35. Deng CL, Guo SM, Xie YX, Li JH. Mild and ligand-free palladium-catalyzed cross-couplings between aryl halides and arylboronic acids for the synthesis of biaryls and heterocycle-containing biaryls. Eur J Org Chem, 2007, 2007: 1457–1462

    Article  Google Scholar 

  36. Leadbeater NE, Marco M. Ligand-free palladium catalysis of the Suzuki reaction in water using microwave heating. Org Lett, 2002, 4: 2973–2976

    Article  CAS  Google Scholar 

  37. Kumbhar A, Kamble S, Mane A, Jha R, Salunkhe R. Modified zeolite immobilized palladium for ligand-free Suzuki-Miyaura cross-coupling reaction. J Organomet Chem, 2013, 738: 29–34

    Article  CAS  Google Scholar 

  38. Wang JQ, Hu L, Cao XQ, Lu JM, Li XM, Gu HW. Catalysis by Pd nanoclusters generated in situ of high-efficiency synthesis of aromatic azo compounds from nitroaromatics under H2 atmosphere. RSC Adv, 2013, 3: 4899–4902

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China

    Bin Luo, JiaQing Wang, DanHua Ge, XinMing Li, XueQin Cao, Yue Pan & HongWei Gu

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  1. Bin Luo
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  2. JiaQing Wang
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  3. DanHua Ge
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  4. XinMing Li
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  5. XueQin Cao
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  6. Yue Pan
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  7. HongWei Gu
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Correspondence to HongWei Gu.

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Luo, B., Wang, J., Ge, D. et al. Efficient and ligand free palladium catalyst for Suzuki and Heck cross-coupling reactions. Sci. China Chem. 57, 1310–1314 (2014). https://doi.org/10.1007/s11426-014-5111-1

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  • DOI: https://doi.org/10.1007/s11426-014-5111-1

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