Chemical Papers

, Volume 73, Issue 4, pp 965–975 | Cite as

Metal-free chemoselective reduction of nitroaromatics to anilines via hydrogen transfer strategy

  • Qi Shuai
  • Jun Li
  • Feng Zhao
  • Weike SuEmail author
  • Guojun DengEmail author
Original Paper


A novel protocol for chemoselective reduction of aromatic nitro compounds to aromatic amines has been established. The metal-free reduction goes through a hydrogen transfer process. Various easily reducible functional groups can be well tolerated under the optimized reaction conditions.


Metal-free Chemoselective reduction Nitrobenzene Elemental sulfur 



This work was supported by the National Natural Science Foundation of China (21172185, 21372187, 21606202).

Supplementary material

11696_2018_634_MOESM1_ESM.doc (2.2 mb)
Supplementary material 1 (DOC 2287 kb)


  1. Ankner T, Hilmersson G (2007) Instantaneous SmI2/H2O/amine mediated reduction of nitroalkanes and α, β-unsaturated nitroalkenes. Tetrahedron Lett 48:5707–5710. CrossRefGoogle Scholar
  2. Arnold H, Dobert F, Gaube J (2008) In handbook of heterogeneous catalysis. Wiley-Interscience, New York, pp 3266–3284Google Scholar
  3. Bae JW, Cho YJ, Lee SH, Yoon COM, Yoon CM (2000) Aone-pot synthesis of N-alkylaminobenzenes from nitroaromatics: reduction followed by reductive amination using B10H14. Chem Commun 19:1857–1858. CrossRefGoogle Scholar
  4. Basu MK, Becker FF, Banik BK (2000) Ultrasound promoted highly efficient reduction of aromatic nitro compounds to the aromatic amines by samarium/ammonium chloride. Tetrahedron Lett 41:5603–5606. CrossRefGoogle Scholar
  5. Berthold H, Schotten T, Honig H (2002) Transfer hydrogenation in ionic liquids under microwave irradiation. Synthesis 11:1607–1610. Google Scholar
  6. Blaser HU (2006) A golden boost to an old reaction. Science 313:312–313. CrossRefGoogle Scholar
  7. Blaser HU, Siegrist U, Steiner H, Studer M, Sheldon RA (2001) Fine chemicals through heterogeneous catalysi-sed. Wiley, Weinheim, p 389Google Scholar
  8. Brinkman HR, Miles WH, Hilborn MD, Smith MC (1996) The reduction of nitrobenzenes by triethylsilane using Wilkinson’s catalyst. Synth Commun 26:973–980. CrossRefGoogle Scholar
  9. Cantillo D, Baghbanzadeh M, Kappe CO (2012) In situ generated iron oxide nanocrystals as efficient and selective catalysts for the reduction of nitroarenes using a continuous flow method. Angew Chem Int Ed 51:210190–210193. CrossRefGoogle Scholar
  10. Cantillo D, Moghaddam MM, Kappe CO (2013) Hydrazine mediated reduction of nitro and azide functionalities catalyzed by highly active and reusable magnetic iron oxide nanocrystals. J Org Chem 78:4530–4542. CrossRefGoogle Scholar
  11. Chandrappa S, Vinaya K, Ramakrishnappa T, Rangappa KS (2010) An efficient method for aryl nitro reduction and cleavage of azo compounds using iron powder/calcium chloride. Synlett 20:3019–3022. Google Scholar
  12. Chen Y, Qiu J, Wang X, Xiu J (2006) Preparation and application of highly dispersed gold nanoparticles supported on silica for catalytic hydrogenation of aromatic nitro compounds. J Catal 242:227–230. CrossRefGoogle Scholar
  13. Chinnappan A, Kim H (2013) Transition metal based ionic liquid (bulk and nanofiber composites) used as catalyst for reduction of aromatic nitro compounds under mild conditions. RSC Adv 3:3399–3406. CrossRefGoogle Scholar
  14. Corma A, Serna P (2006) Chemoselective hydrogenation of nitro compounds with supported gold catalysts. Science 313:332–334. CrossRefGoogle Scholar
  15. Corma A, Serna P, Concepcion P, Calvino JJ (2008) Transforming nonselective into chemoselective metal catalysts for the hydrogenation of substituted nitroaromatics. J Am Chem Soc 130:8748–8753. CrossRefGoogle Scholar
  16. Cui X, Zhang Y, Shi F, Deng Y (2011) Ruthenium catalyze nitro and nitrile compounds coupling with alcohols: alternative route for N-substituted amine Synthesis. Chem. Eur. J 17:2587–2591. CrossRefGoogle Scholar
  17. Desai DG, Swami SS, Dabhade SK, Ghagare MG (2001) FeS–NH4Cl–CH3OH–H2O: an efficient and inexpensive system for reduction of nitroarenes to anilines. Synth Commun 31:1249–1251. CrossRefGoogle Scholar
  18. Feng C, Liu Y, Peng S, Shuai Q, Deng G, Li C-J (2010) Ruthenium catalyzed tertiary amine formation from nitroarenes and alcohols. Org Lett 12:4888–4891. CrossRefGoogle Scholar
  19. Gallagher WP, Marlatt M, Livingston R, Kiau S, Muslehiddinoglu J (2012) The development of a scalable, chemoselective nitro reduction. Org Process Res Dev 16:1665–1668. CrossRefGoogle Scholar
  20. Gamble AB, Garner J, Gordon CP, O’Conner SMJ, Keller PA (2007) Aryl nitro reduction with iron powder or stannous chloride under ultrasonic irradiation. Synth Commun 37:2777–2786. CrossRefGoogle Scholar
  21. Gawande MB, Guo H, Rathi AK, Branco PS, Chen Y, Rajender S, Varmad RS, Peng DL (2013) First application of core shell Ag@Ni magnetic nanocatalyst for transfer hydrogenation reactions of aromatic nitro and carbonyl compounds. RSC Adv 3:1050–1054. CrossRefGoogle Scholar
  22. Guillena G, Ramon DJ, Yus M (2010) Hydrogen autotransfer in the N-Alkylation of amines and related compounds using alcohols and amines as electrophiles. Chem Rev 110:1611–1641. CrossRefGoogle Scholar
  23. Haber F (1898) About gradual reduction of the nitrobenzene with limited cathode potential. Zeitschrift fuer Ele-ktrochemie und Angewandte Physikalische Chemie 22:506–513. Google Scholar
  24. He L, Wang LC, Sun H, Ni J, Cao Y, He HY, Fan KN (2009) Efficient and selective room temperature gold catalyzed reduction of nitro compounds with co and H2O as the hydrogen source. Angew Chem Int Ed 48:9538–9541. CrossRefGoogle Scholar
  25. Jagadeesh RV, Wienhoefer G, Westerhaus FA, Surkus AE, Pohl MM, Junge H, Junge K, Beller M (2011) Efficient and highly selective iron catalyzed reduction of nitroarenes. Chem Commun 47:10972–10974. CrossRefGoogle Scholar
  26. Jagadeesh RV, Surkus AE, Junge H, Pohl MM, Radnik J, Rabeah J, Huan H, Schuenemann V, Brueckner A, Beller M (2013) Nanoscale Fe2O3 based catalysts for selective hydrogenation of nitroarenes to anilines. Science 342:1073–1076. CrossRefGoogle Scholar
  27. Jagadeesh RV, Banerjee D, Arockiam PB, Junge H, Junge K, Pohl MM, Radnik J, Brueckner A, Beller M (2015) Highly selective transfer hydrogenation of functionalised nitroarenes using cobalt based nanocatalysts. Green Chem 17:898–902. CrossRefGoogle Scholar
  28. Junge K, Wendt B, Shaikh N, Beller M (2010) Iron catalyzed selective reduction of nitroarenes to anilines using organosilanes. Chem Commun 46:1769–1777. CrossRefGoogle Scholar
  29. Kabalka GW, Varma RS (1991) Reduction of nitro and nitroso compounds. In: Trost BM, Fleming I (eds) Comprehensive organic synthesis, vol 8, 1st edn. Pergamon Press, Oxford, p 363CrossRefGoogle Scholar
  30. Kelly SM, Lipshutz BH (2014) Chemoselective reductions of nitroaromatics in water at room temperature. Org Lett 16:98–101. CrossRefGoogle Scholar
  31. Khan FA, Dash J, Sudheer C, Gupta RK (2003) Chemoselective reduction of aromatic nitro and azo compounds in ionic liquids using zinc and ammonium salts. Tetrahedron Lett 44:7783–7787. CrossRefGoogle Scholar
  32. Kim S, Kim E, Kim BM (2011) Fe3O4 nanoparticles a conveniently reusable catalyst for the reduction of nitroarenes using hydrazine hydrate. Chem Asian J 6:1921–1925. CrossRefGoogle Scholar
  33. Kim JH, Park JH, Chung YK, Park KH (2012) Ruthenium nanoparticle-catalyzed, controlled and chemoselective hydrogenation of nitroarenes using ethanol as a hydrogen source. Adv Synth Catal 354:2412–2418. CrossRefGoogle Scholar
  34. Kumarraja M, Pitchumani K (2004) Simple and efficient reduction of nitroarenes by hydrazine in Faujasite zeolites. Appl Catal A 265:135–139. CrossRefGoogle Scholar
  35. Kumbha PS, Sanehez-Valente J, Figueras F (1998) Reduction of aromatic nitro compounds with hydrazine hydrate in the presence of the lron(III) oxide-MgO catalyst prepared from a Mg–Fe hydrotalcite precursor. Tetrahedron Lett 39:2573–2574. CrossRefGoogle Scholar
  36. Kunfi A, Szabó V, Mastalir A, Bucsi I, Mohai M, NémethP Bertóti I, London G (2017) Palladium on polydopamine: its true potential in catalytic transfer hydrogenations and heck coupling reactions. ChemCatChem 9:3236–3244. CrossRefGoogle Scholar
  37. Lawrence SA (2004) Amines: synthesis properties and applications. Cambridge University Press, CambridgeGoogle Scholar
  38. Leleu S, Papamicae C, Marsais F, Dupas G, Levacher V (2004) Preparation of axially chiral quinolinium salts related to NAD+ models: new investigations of these biomimetic models as chiral amide-transferring agents. Tetrahedron Asymmetry 15:3919–3928. CrossRefGoogle Scholar
  39. Li B, Xu Z (2009) A nonmetal catalyst for molecular hydrogen activation with comparable catalytic hydrogenation capability to noble metal catalyst. J Am Chem Soc 131:16380–16382. CrossRefGoogle Scholar
  40. Li J, Shi XY, Bi YY, Wei JF, Chen ZG (2011) Pd nanoparticles in ionic liquid brush a highly active and reusable heterogeneous catalytic assembly for solvent free or on water hydrogenation of nitroarene under mild conditions. ACS Catal 1:657–664. CrossRefGoogle Scholar
  41. Liu Y, Chen W, Feng C, Deng G (2011) Ruthenium catalyzed one-pot aromatic secondary amine formation from nitroarenes and alcohols. Chem Asian J 6:1142–1146. CrossRefGoogle Scholar
  42. Mahdavi H, Tamami B (2005) Reduction of nitro aryl compounds with zinc in the presence of Poly[N-(2-aminoethyl)acrylamido]-trimethylammonium chloride as a phase-transfer catalyst. Synth Commun 35:1121–1127. CrossRefGoogle Scholar
  43. Maity SK, Pradhan NC, Patwardhan AV (2006) Kinetics of the reduction of nitrotoluenes by aqueous ammonium sulfide under liquid–liquid phase transfer catalysis. Appl Catal A 301:251–258. CrossRefGoogle Scholar
  44. Mazaheri O, Kalbasi RJ (2015) Preparation and characterization of Ni/mZSM-5 zeolite with a hierarchical pore structure by using KIT-6 as silica template: an efficient bi-functional catalyst for the reduction of nitro aromatic compounds. RSC Adv 53:4398–34414. Google Scholar
  45. McLaughlin MA, Barnes DM (2006) A practical and selective reduction of nitroarenes using elemental sulfur and mild base. Tetrahedron Lett 47:9095–9097. CrossRefGoogle Scholar
  46. Mondal U, Puthankot A, Sen S, Singh G (2016) Novelties of triphasic phase transfer catalysed zinin reduction of nitrochlorobenzene by H2S-laden monoethanolamine. RSC Adv 6:23666–23676. CrossRefGoogle Scholar
  47. Motoyama Y, Kamo K, Nagashima H (2009) Catalysis in polysiloxane gels platinum-catalyzed hydrosilylation of polymethylhydrosiloxaneleading to reusable catalysts for reduction of nitroarenes. Org Lett 11:1345–1348. CrossRefGoogle Scholar
  48. Nakamula I, Yamanoi Y, Imaoka T, Yamamoto K, Nishihara H (2011) A uniform bimetallic rhodium/iron nanoparticle catalyst for the hydrogenation of olefins and nitroarenes. Angew Chem Int Ed 50:5830–5833. CrossRefGoogle Scholar
  49. Niknam K, Kiasat AR, Kazemi F, Hossieni A (2003) Efficient reduction of nitroarenes to the corresponding anilines with sulfur in basic media under solvent-free conditions. Phosphorus Sulfur Silicon 178:1385–1389. CrossRefGoogle Scholar
  50. Nishimura S (2001) Handbook of heterogeneous catalytic hydrogenation for organic synthesis. Wiley Interscience, New York, p 784Google Scholar
  51. Nixon TD, Whittlesey MK, Williams JMJ (2009) Transitio-n metal catalysed reactions of alcohols using borrowing hydrogen methodology. Dalton Trans 5:753–762. CrossRefGoogle Scholar
  52. Noronha RG, Romao CC, Fernandes AC (2009) Highly chemo and regioselective reduction of aromatic nitro compounds using the system silane/oxo-rhenium complexes. J Org Chem 74:6960–6964. CrossRefGoogle Scholar
  53. Nugent TC (2010) Chiral amine synthesis: methods, developments and applications. Wiley, WeinheimCrossRefGoogle Scholar
  54. Orlandi M, Brenna D, Harms R, Jost S, Benaglia M (2018) Recent developments in the reduction of aromatic and aliphatic nitro compounds to amines. Org Process Res Dev 22:430–445. CrossRefGoogle Scholar
  55. Pandarus V, Ciriminna R, Beland F, Pagliaro M (2011) A new class of heterogeneous platinum catalysts for the chemoselective hydrogenation of nitroarenes. Adv Synth Catal 353:1306–1316. CrossRefGoogle Scholar
  56. Patai S (1996) The chemistry of amines, nitroso, nitro and related groups. Wiley, ChichesterCrossRefGoogle Scholar
  57. Pehlivan L, Métay E, Laval S, Dayoub W, Demonchaux P, Mignani G, Lemaire M (2010) Iron catalyzed selective reduction of nitro compounds to amines. Tetrahedron Lett 51:1939–1941. CrossRefGoogle Scholar
  58. Pogorelic I, Filipan-Litvic M, Merkas S, Ljubic G, Cepanec I, Litvic M (2007) Rapid, efficient and selective reduction of aromatic nitro compounds with sodium borohydride and raney nickel. J Mol Catal A Chem 274:202–207. CrossRefGoogle Scholar
  59. Rahaim RJ, Maleczka RE (2005) Pd-catalyzed silicon hydride reductions of aromatic and aliphatic nitro groups. Org Lett 7:5087–5090. CrossRefGoogle Scholar
  60. Rahaim RJ, Maleczka RE (2006) Palladium-catalyzed silane/siloxane reductions in the one-pot conversion of nitro compounds into their amines, hydroxylamines, amides, sulfonamides, and carbamates. Synthesis 19:3316–3340. Google Scholar
  61. Rai RK, Mahata A, Mukhopadhyay S, Gupta S, Li PZ, Nguyen KT, Zhao Y, Pathak B, Singh SK (2014) Room temperature chemoselective reduction of nitro groups using non-noble metal nanocatalysts in water. Inorg Chem 53:2904–2909. CrossRefGoogle Scholar
  62. Ricci A (2008) Amino group chemistry: from synthesis to the life sciences. Wiley, WeinheimGoogle Scholar
  63. Saha A, Ranu B (2008) Highly Chemoselective reduction of aromatic nitro compounds by copper nanoparticles ammonium formate. J Org Chem 73:6867–6870. CrossRefGoogle Scholar
  64. Sharma U, Kumar P, Kumar N, Kumar V, Singh B (2010) Highly chemo and regioselective reduction of aromatic nitro compounds catalyzed by recyclable Copper(II) as well as Cobalt(II) phthalocyanines. Adv Synth Catal 352:1834–1840. CrossRefGoogle Scholar
  65. Sharma U, Verma PK, Kumar N, Kumar V, Bala M, Singh B (2011) Phosphane-free green protocol for selective nitro reduction with an iron-based catalyst. Chem Eur J 17:5903–5907. CrossRefGoogle Scholar
  66. Sharma S, Kumar M, Kumar V, Kumar N (2014) Metal Free transfer hydrogenation of nitroarenes in water with vasicine: revelation of organocatalytic facet of an abundant alkaloid. J Org Chem 79:9433–9439. CrossRefGoogle Scholar
  67. Shi Q, Lu R, Jin K, Zhang Z, Zhao D (2006) Simple and ecofriendly reduction of nitroarenes to the corresponding aromatic amines using polymer-supported hydrazine hydrate over iron oxide hydroxide catalyst. Green Chem. Google Scholar
  68. Shi X, Wang X, Shang X, Zou X, Ding W, Lu X (2017) High performance and active sites of a ceria supported palladium catalyst for solvent free chemoselective hydrogenation of nitroarenes. ChemCatChem 9:3743–3751. CrossRefGoogle Scholar
  69. Sorribes I, Wienhoefer G, Vicent C, Junge K, Llusar R, Beller M (2012) Chemoselective transfer hydrogenation to nitroarenes mediated by cubane type Mo3S4 cluster catalysts. Angew Chem Int Ed 51:7794–7798. CrossRefGoogle Scholar
  70. SuwiBski J, Wagner P (1996) Reduction of aromatic nitrocompounds by sodium borohydride in methanol in the presence of sodium methoxide. Tetrahedron 52:9541–9552. CrossRefGoogle Scholar
  71. Takasaki M, Motoyama Y, Higashi K, Yoon SH, Mochida I, Nagashima H (2008) Chemoselective hydrogenation of nitroarenes with carbon nanofiber-supported platinum and palladium nanoparticles. Org Lett 10:1601–1604. CrossRefGoogle Scholar
  72. Tang CH, He L, Liu YM, Cao Y, He HY, Fan KN (2011) Direct one-pot reductive N-alkylation of nitroarenes by using alcohols with supported gold catalysts. Chem Eur J 17:7172–7177. CrossRefGoogle Scholar
  73. Ullmann F (2012) Ullmann’s encyclopedia of industrial chemistry, vol A2. Verlag Chemie, Weinheim, pp 647–718Google Scholar
  74. Vass A, Dudas J, Toth J, Varma RS (2001) Solvent free reduction of aromatic nitro compounds with alumina supported hydrazine under microwave irradiation. Tetrahedron Lett. 42:5347–5349. CrossRefGoogle Scholar
  75. Wang J, Yuan Z, Nie R, Hou Z, Zheng X (2010) Hydrogenation of nitrobenzene to aniline over silica gel supported nickel catalysts. Ind Eng Chem Res 49:4664–4669. CrossRefGoogle Scholar
  76. Wang X, Cárdenas-Lizana F, Keane MA (2014) Toward sustainable chemoselective nitroarene hydrogenation using supported gold as catalyst. ACS Sustain Chem Eng 2:2781–2789. CrossRefGoogle Scholar
  77. Watson AJA, Williams JMJ (2010) The Give and Take of Alcohol Activation. Science 329:635–636. CrossRefGoogle Scholar
  78. Wienhoefer G, Sorribes I, Boddien A, Westerhaus F, JungeK Junge H, Llusar R, Beller M (2011) General and selective iron catalyzed transfer hydrogenation of nitroarenes without base. J Am Chem Soc 133:12875–12879. CrossRefGoogle Scholar
  79. Wu H, Zhuo L, He Q, Liao X, Shi B (2009) Heterogeneous hydrogenation of nitrobenzenes over recyclable Pd(0) nanoparticle catalysts stabilized by polyphenol grafted collagen fibers. Appl Catal 366:44–56. CrossRefGoogle Scholar
  80. Xie Y, Liu S, Liu Y, Wen Y, Deng GJ (2012) Palladium catalyzed one pot diarylamine formation from nitroarenes and cyclohexanones. Org Lett 14:1692–1695. CrossRefGoogle Scholar
  81. Yadav GD, Jadhav YB, Sengupta S (2003) Novelties of kinetics and mechanism of liquid–liquid phase transfer catalysed reduction of p-nitroanisole to p-anisidine. Chem Eng Sci 58:2681–2689. CrossRefGoogle Scholar
  82. Yamane Y, Liu X, Hamasaki A, Ishida T, Haruta M, Yokoyama T, Tokunaga M (2009) One-pot synthesis of indoles and aniline derivatives from nitroarenes under hydrogenation condition with supported gold nano-particles. Org Lett 11:5162–5165. CrossRefGoogle Scholar
  83. Yang XJ, Chen B, Zheng LQ, Wu LZ, Tung CH (2014) Highly efficient and selective photocatalytic hydrogenation of functionalized nitrobenzenes. Green Chem 16:1082–1086. CrossRefGoogle Scholar
  84. Zhou YH, Yang Q, Chen YZ, Jiang HL (2017) Low-cost CuNiMIL-101 as an excellent catalyst toward cascade reaction integration of ammonia borane dehydrogenation with nitroarene hydrogenation. Chem Commun 53:12361–12364. CrossRefGoogle Scholar
  85. Zimmermann V, Avemaria F, Brase S (2007) Chemoselective reduction of nitroarenes in the presence of acid-sensitive functional groups: solid phase syntheses of amino aryl azides and benzotriazoles. J Comb Chem 9:200–203. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2018

Authors and Affiliations

  1. 1.Collaborative Innovation Center of Yangtze River Delta Region Green PharmaceuticalsZhejiang University of TechnologyHangzhouChina
  2. 2.College of Pharmaceutical SciencesZhejiang University of TechnologyHangzhouChina
  3. 3.Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of ChemistryXiangtan UniversityXiangtanChina

Personalised recommendations