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Transfer hydrogenation using recyclable polymer-supported formate (PSF): Efficient and chemoselective reduction of nitroarenes

Summary

Nitroarenes can be reduced in high yields to the corresponding anilines by transfer hydrogenation using a stable H-donor, polymer-supported formate (PSF) in combination with palladium acetate (catalytic). The reactions occur at 100–120C in dimethyl-formamide and the PSF can be recycled for at least three runs. The procedure is chemoselective for nitro group; ester, ketone, aldehyde, and halide substituents on aromatic ring remain unaffected.

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References

  1. Larock, R.C., Comprehensive Organic Transformations: A Guide to Functional Group Preparations, Wiley-VCH, New York, 1999, pp. 823–827.

    Google Scholar 

  2. Sandler, S.R. and Karo, W., Organic Functional Group Preparation, Academic Press, New York, 1968, pp. 339–345.

    Google Scholar 

  3. Kabalka, G.W. and Verma, R.S., Reduction of nitro and nitroso compounds, In Trost, B.M. and Fleming, E. (Eds.) Comprehensive Organic Synthesis, Vol. 8, Pergamon Press, Oxford, 1991, pp. 363–379.

    Google Scholar 

  4. Hudlicky, M., Reductions in Organic Chemistry, American Chemical Society, Washington DC, 1996.

    Google Scholar 

  5. Lewis, P.A. (Ed.), Pigment Handbook, Wiley, New York, 1988; Vol 1.

    Google Scholar 

  6. Negwer, M., Organic-Chemical Drugs and Their Synonyms (An International Survey); 7th Ed., Akademie Verlag GmbH, Berlin, 1994.

    Google Scholar 

  7. Montogomery, J.H., Agrochemicals Desk Reference: Environmental Data, Lewis Publishers, Chelsea, MI, 1993.

    Google Scholar 

  8. D'Aproano, G., Schiavon, G., Zotti, G. and Leclere, M., Synthesis and characterization of polyaniline derivatives: Poly(2-alkoxyanilines) and poly(2,5-dialkoxyanilines), Chem. Mater., 7 (1995) 33– 42.

    Google Scholar 

  9. Solomons, T.W.G., Organic Chemistry, 6th Ed., Wiley, New York, 1996, pp. 925–932.

    Google Scholar 

  10. Rylander, P., Catalytic Hydrogenation in Organic Synthesis, Academic Press, New York, 1979.

    Google Scholar 

  11. Ono, N., The Nitro Group in Organic Synthesis, Wiley-VCH, New York, 2001, pp. 170–172.

    Google Scholar 

  12. Hartman, W.W., Dickey, J.B. and Stampfli, J.G., 2,6-Dibromoquinone-4-chloroimide, Org. Synth., 2 (1943) 175–177.

    Google Scholar 

  13. Fox, B.A. and Threlfall, T.L., 2,6-Diaminopyridine, Org. Synth., 5 (1973) 346–351.

    Google Scholar 

  14. Wertheim, E., Orthanilic acid, Org. Synth., 2 (1943) 471–473.

    Google Scholar 

  15. Moody, C.J. and Pitts, M.R., Indium as a reducing agent: Reduction of aromatic nitro groups, Synlett, (1998) 1028.

  16. Banik, B.K., Mukhopadhyay, C., Venkattaman, M.S. and Becker, F.F., A facile reduction of aromatic nitro compounds to aromatic amines by samarium and iodine, Tetrahedron Lett., 39 (1998) 7243–7246.

    CAS  Google Scholar 

  17. Basu, M.K., Becker, F.F. and Banik, B.K., Ultrasound-promoted highly efficient reduction of aromatic nitro compounds to the aromatic amines by samarium/ammonium chloride, Tetrahedron Lett., 41 (2000) 5603–5606.

    Article  CAS  Google Scholar 

  18. Braude, E.A. and Linstead, R.P., Hydrogen transfer. Part I. Introductory survey, J. Chem. Soc., (1954) 3544–3547.

  19. Brieger, G. and Nestrick, T.J., Catalytic transfer hydrogenation, Chem. Rev., 74 (1974) 567–580.

    Article  CAS  Google Scholar 

  20. Johnstone, R.A.W., Wilby, A.H. and Entwistle, I.D., Homogeneous catalytic transfer hydrogenation and its relation to other methods for reduction of organic compounds, Chem. Rev., 85 (1985) 129– 170.

    Article  CAS  Google Scholar 

  21. Gowda, B., Mahesh, B. and Shankare, G., Zinc-Catalyzed Ammonium Formate Reductions: Reduction of Nitro Compounds, Ind. J. Chem. Sect. B, 40 (2001) 75–77 and references cited therein.

  22. Bhaumik, K. and Akamanchi, K.G., Nitroarene reduction using Raney nickel alloy with ammonium chloride in water, Can. J. Chem., 81 (2003) 197–198.

    Article  CAS  Google Scholar 

  23. Ram, S. and Ehrenkaufer, R.E., Ammonium formate in organic Synthesis: A versatile agent in catalytic hydrogen transfer reductions. Synthesis, (1988) 91–95.

  24. Pratap, T.V. and Baskaran, S., Direct conversion of aryl nitro compounds to formanilides under catalytic transfer hydrogenation conditions, Tetrahedron Lett., 42 (2001) 1983–1985.

    Article  CAS  Google Scholar 

  25. Obrecht, D. and Villalgordo, J.M., Solid-Supported Combinatorial and Parallel Synthesis of Small Molecular-Weight Compound Libraries, Pergamon, Oxford, 1998.

    Google Scholar 

  26. Terrett, N.K., Combinatorial Chemistry, Oxford University Press, Oxford, 1998.

    Google Scholar 

  27. Brown, A.R., Hermkenes, P.H.H., Ottenheijm, H.C.J. and Rees, D.C., Solid phase synthesis, Synlett, (1998) 817–827.

  28. Kirschning, A., Monenschein, H. and Wittenberg, R., Functionalized polymers–emerging versatile tools for solution-phase chemistry and automated parallel synthesis, Angew. Chem. Int. Ed. Engl., 40 (2001) 650–679 and references cited therein.

  29. Zaragoza Dorwald, F., Organic Synthesis on Solid Support, Wiley-VCH, Weinheim, 2000.

    Google Scholar 

  30. Kirschning, A., Borohydride Exchange Resins (BER) —a Group of versatile and powerful polymer-supported reductants, J. Prakt. Chem., 342 (2000) 508–511.

    Article  CAS  Google Scholar 

  31. Basu, B., Bhuiyan, M.M.H. and Jha, S., Palladium mediated chemoselective reduction of α,β-unsaturated cyano esters with potassium formate, Synth. Commun., 33 (2003) 291–296.

    Article  CAS  Google Scholar 

  32. Basu, B., Jha, S., Bhuiyan, M.M.H. and Das, P., A simple protocol for direct reductive amination of aldehydes and ketones using potassium formate and catalytic palladium acetate, Synlett, (2003) 555–557.

  33. Basu, B., Bhuiyan, M.M.H., Das, P. and Hossain, I., Catalytic transfer reduction of conjugated alkenes and an imine using polymer-supported formates, Tetrahedron Lett., 44 (2003) 8931–8934.

    CAS  Google Scholar 

  34. Banik, B.K., Barakat, K.J., Wagle, D.R., Manhas, M.S. and Bose, A.K., Microwave-assisted rapid and simplified hydrogenation, J. Org. Chem., 64 (1999) 5746–5753.

    Article  CAS  Google Scholar 

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Correspondence to Basudeb Basu.

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Basu, B., Das, P. & Das, S. Transfer hydrogenation using recyclable polymer-supported formate (PSF): Efficient and chemoselective reduction of nitroarenes. Mol Divers 9, 259–262 (2005). https://doi.org/10.1007/s11030-005-8106-1

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  • DOI: https://doi.org/10.1007/s11030-005-8106-1

Key Words

  • aniline
  • ion-exchange resin
  • nitroarene
  • palladium acetate
  • polymer-supported formate
  • transfer hydrogenation