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Palladium oxide nanofibers: an efficient catalyst for cross-coupling of challenging aromatic nitriles

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Abstract

Heterogeneous catalysis is a promising method in industry to synthesis bioactive molecules, fine chemicals and pharmaceuticals. Particularly, cross-coupling reactions using transition metal catalyst are the hot topic of research in recent period due to its efficiency. Nanofibers are most preferred for this purpose due to its huge surface area, easy separation and minimum catalyst loading. Herein, we are reporting palladium oxide nanofibers (PdO NF) of 75 nm, prepared by electrospinning technique, as catalyst for the cross-coupling of challenging bromo, chloro and fluoro benzonitriles. The successfulness of the present catalytic system was evidenced from the coupling products (confirmed by 1H&13C NMR) of the most reluctant fluoro benzonitriles. Furthermore, possible mechanism for the rapid formation was proposed based on the products and literature reports. In addition to the above, heterogeneity and metal leaching was verified (by GC-MS and ICP-MS) with the aim to scale up the process.

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References

  • Alonso DA, Nájera C, Pacheco MC (2002) Highly active oxime-derived Palladacycle complexes for Suzuki− Miyaura and Ullmann-type coupling reactions. J Organ Chem 67(16):5588–5594

    Article  CAS  Google Scholar 

  • Arumugam V, Kaminsky W, Bhuvanesh NS, Nallasamy D (2015) Palladium (II) complexes containing ONO tridentate hydrazone for Suzuki-Miyaura coupling of aryl chlorides in aqueous-organic media. RSC Adv 5(73):59428–59436

    Article  CAS  Google Scholar 

  • Badone D, Baroni M, Cardamone R, Ielmini A, Guzzi U (1997) Highly efficient palladium-catalyzed boronic acid coupling reactions in water: scope and limitations. J Organ Chem 62(21):7170–7173

    Article  CAS  Google Scholar 

  • Biffis A, Centomo P, Del Zotto A, Zecca M (2018) Pd metal catalysts for cross-couplings and related reactions in the 21st century: a critical review. Chem Rev 118(4):2249–2295

    Article  CAS  PubMed  Google Scholar 

  • Billingsley K, Buchwald SL (2007) Highly efficient monophosphine-based catalyst for the palladium-catalyzed suzuki− miyaura reaction of heteroaryl halides and heteroaryl boronic acids and esters. J Am Chem Soc 129(11):3358–3366

    Article  CAS  PubMed  Google Scholar 

  • Blond CRL, Andrews AT, Sun Y, Sowa JR (2001) Activation of aryl chlorides for Suzuki cross-coupling by ligandless, heterogeneous palladium. Organ Lett 3(10):1555–1557

    Article  Google Scholar 

  • Bradshaw M, Zou J, Byrne L, Iyer KS, Stewart SG, Raston CL (2011) Pd (II) conjugated chitosan nanofibre mats for application in Heck cross-coupling reactions. Chem Commun 47(45):12292–12294

    Article  CAS  Google Scholar 

  • Erami RS, Díaz-García D, Prashar S, Rodríguez-Diéguez A, Fajardo M, Amirnasr M, Gómez-Ruiz S (2017) Suzuki-Miyaura CC coupling reactions catalyzed by supported Pd nanoparticles for the preparation of fluorinated biphenyl derivatives. Catalysts 7(3):76

    Article  Google Scholar 

  • Gallon BJ, Kojima RW, Kaner RB, Diaconescu PL (2007) Palladium nanoparticles supported on polyaniline nanofibers as a semi-heterogeneous catalyst in water. Angew Chem Int Ed 46:7251–7254

    Article  CAS  Google Scholar 

  • Geng X, Luo Y, Zheng B, Zhang C (2017) Photon assisted room-temperature hydrogen sensors using PdO loaded WO3 nanohybrids. Int J Hydrogen Energy 42(9):6425–6434

    Article  CAS  Google Scholar 

  • Ghosh R, Adarsh NN, Sarkar A (2010) A novel, air-stable phosphine ligand for the palladium-catalyzed Suzuki− Miyaura cross-coupling reaction of chloro arenes. J Organ Chem 75(15):5320–5322

    Article  CAS  Google Scholar 

  • Hussain I, Capricho J, Yawer MA (2016) Synthesis of Biaryls via Ligand-Free Suzuki-Miyaura cross-coupling reactions: a review of homogeneous and heterogeneous catalytic developments. Adv Synthes Catal 358(21):3320–3349

    Article  CAS  Google Scholar 

  • Karanjit S, Kashihara M, Nakayama A, Shrestha LK, Ariga K, Namba K (2018) Highly active and reusable hydrotalcite-supported Pd (0) catalyst for Suzuki coupling reactions of aryl bromides and chlorides. Tetrahedron 74:948–954

    Article  CAS  Google Scholar 

  • Martin R, Buchwald SL (2008) Palladium-catalyzed Suzuki− Miyaura cross-coupling reactions employing dialkylbiaryl phosphine ligands. Accoun Chem Res 41(11):1461–1473

    Article  CAS  Google Scholar 

  • Miyaura N, Ishiyama T, Sasaki H, Ishikawa M, Sato M, Suzuki A (1989) Palladium-catalyzed inter-and intramolecular cross-coupling reactions of B-alkyl-9-borabicyclo [3.3. 1] nonane derivatives with 1-halo-1-alkenes or haloarenes. Syntheses of functionalized alkenes, arenes, and cycloalkenes via a hydroboration-coupling sequence. J Am Chem Soc 111(1):314–321

    Article  CAS  Google Scholar 

  • Pérez-Lorenzo M (2012) Palladium nanoparticles as efficient catalysts for Suzuki cross-coupling reactions. J Phys Chem Letters 3(2):167–174

    Article  Google Scholar 

  • Phan NT, Van Der Sluys M, Jones CW (2006) On the nature of the active species in palladium catalyzed Mizoroki-Heck and Suzuki-Miyaura couplings–homogeneous or heterogeneous catalysis, a critical review. Adv Synthes Catal 348(6):609–679

    Article  CAS  Google Scholar 

  • Rajabi F, Fayyaza F, Bandyopadhyay R, Ivars-Barcelo F, Puente-Santiago AR, Luque R (2018) Cytosine palladium hybrid complex immobilized on SBA-15 as efficient heterogeneous catalyst for the aqueous suzuki-miyaura coupling. Chem Select 3:6102–6106

    CAS  Google Scholar 

  • Schlögl R, Abd Hamid SB (2004) Nanocatalysis: Mature science revisited or something really new? Angewandte Chemie International Edition 43(13):1628–1637

    Article  PubMed  Google Scholar 

  • Suzuki A (1991) Synthetic studies via the cross-coupling reaction of organoboron derivatives with organic halides. Pure Appl Chem 63(3):419–422

    Article  CAS  Google Scholar 

  • Thenmozhi S, Kadirvelu K (2018) Transfer hydrogenation and hydration of aromatic aldehydes and nitriles using heterogeneous NiO nanofibers as a catalyst. New J Chem 42(19):15572–15577

    Article  CAS  Google Scholar 

  • Tobisu M, Xu T, Shimasaki T, Chatani N (2011) Nickel-catalyzed Suzuki-Miyaura reaction of aryl fluorides. J Am Chem Soc 133(48):19505–19511

    Article  CAS  PubMed  Google Scholar 

  • Wang K, Wang W, Luo H, Zheng X, Fu H, Chen H, Li R (2013) An Easily Prepared Tetraphosphine and Its Use in the Palladium-Catalyzed Suzuki-Miyaura Coupling of Aryl Chlorides. Catal Lett 143:1214–1219

    Article  CAS  Google Scholar 

  • Wang T, Tao X, Wu D, Lu X, Yu Q, Liu S, Chen H, Li B (2020) High activity and stability of PdO x anchored in porous NiO nanofibers for catalyzing Suzuki coupling reactions. J Phys Chem C 124(41):22539–22549

    Article  CAS  Google Scholar 

  • Wilson AA, Corby S, Francas L, Durrant JR, Kafizas A (2021) The effect of nanoparticulate PdO co-catalysts on the faradaic and light conversion efficiency of WO 3 photoanodes for water oxidation. Phys Chem Chem Phys 23(2):1285–1291

    Article  CAS  PubMed  Google Scholar 

  • Wolfe JP, Buchwald SL (1999) A highly active catalyst for the room-temperature amination and Suzuki coupling of aryl chlorides. Angew Chem Int Ed 38(16):2413–2416

    Article  CAS  Google Scholar 

  • Yin J, Buchwald SL (2000) A catalytic asymmetric Suzuki coupling for the synthesis of axially chiral biaryl compounds. J Am Chem Soc 122(48):12051–12052

    Article  CAS  Google Scholar 

  • Zhao YL, Li Y, Li SM, Zhou YG, Sun FY, Gao LX, Han FS (2011) A highly practical and reliable nickel catalyst for Suzuki-Miyaura coupling of aryl halides. Adv Synthes Catal 353(9):1543–1550

    Article  CAS  Google Scholar 

  • Zhou W, Guan Y, Wang D, Zhang X, Liu D, Jiang H, Wang J, Liu X, Liu H, Chen S (2014) PdO/TiO2 and Pd/TiO2 heterostructured nanobelts with enhanced photocatalytic activity. Chem Asian J 9(6):1648–1654

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

The authors thank Defence Research and Development Organisation (DRDO) for the financial support and acknowledge the major scientific contribution of Dr.N.Dharmaraj. One of the authors (S.T) thanks Dr.P.Kalimuthu of Gandhigram University for NMR analysis.

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Correspondence to K. Kadirvelu.

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Thenmozhi, S., Dharmaraj, N. & Kadirvelu, K. Palladium oxide nanofibers: an efficient catalyst for cross-coupling of challenging aromatic nitriles. Chem. Pap. 77, 3911–3920 (2023). https://doi.org/10.1007/s11696-023-02751-1

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