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Progress in Chemistry 2020, Vol. 32 Issue (1): 72-83 DOI: 10.7536/PC190501 Previous Articles   Next Articles

Reductive Amination of Nitroarenes and Alcohols: Catalyst and Catalytic Mechanism

Ping Yang, Minjie Liu, Hao Zhang, Wenting Guo, Chaoyang Lv, Di Liu**()   

  1. 1. College of Chemical and Biological Engineering, Shandong University of Science and Technology, Qingdao 266590, China
  • Received: Online: Published:
  • Contact: Di Liu
  • About author:
    ** E-mail:
  • Supported by:
    National Natural Science Foundation of China(21878178)
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Amine compounds have been widely applied in the field of pharmaceuticals, dyes and fine chemicals due to its characteristics of chemical structure and property. Many methods for the synthesis of amine compounds are available, in which the reductive amination of nitroarenes and alcohols has attracted extensive attention because nitroarenes and alcohols with the advantages of good accessibility and stable chemical properties can directly be converted to amines by one-pot method without additional hydrogen sources. The recent progress is summarized from two aspects: catalyst and catalytic mechanism based on reaction pathways of the reductive amination of nitroarenes in this article. We introduce all kinds of catalytic systems in detail such as noble metal, photocatalyst, and so on, the catalytic performance, applicability and catalytic mechanism of which are highlighted. It needs to be pointed out that these catalytic systems show varying degrees of success as well as limitations like high cost of catalyst, narrow applicable range of substrates, excessive exogenous base, additional hydrogen source and/or toxic organic solvents. Based on the above problems, it would be desirable to develop a green, efficient, inexpensive and universal catalytic system, the catalytic mechanism of various catalysts should be systematically studied to provide guidance for the development of catalytic system on the other hand.

Key words: nitrobenzenes, alcohols, reductive amination, amines, noble-metal, photocatalyst, catalytic mechanism
Fig. 1 Current methods for synthesizing amine compounds
Table 1 Catalytic condensation of primary alcohols and nitroarenesa [12]
Entry R1 R2 t(h) Product Yield (%)b
1 4-Me C6H5 3 83
2 4-MeO C6H5 3 55
3 H 4-Me-C6H5 5 90
4 H 4-MeO-C6H5 20 50(43)
5 H C6H5CH=CHCH2 20 17
6 H C6H5CH2 12 92
7 H C6H5 3 82
8 4-Me 4-Me-C6H5 12 89
9 4-Me 4-MeO-C6H5 12 83
10 4-MeO C6H5 3 75
11 4-MeO 4-Me-C6H5 12 84
12 4-MeO 4-MeO-C6H5 12 70(65)
Fig. 2 Catalyzed tandem reaction between nitrobenzene and benzyl alcohol: (a) two pathways in the reduction of nitroarene; (b) alcohol oxidation, and (c) amine/aldehyde condensation products[13]
Fig. 3 Proposed reaction mechanism[18]
Fig. 4 The plausible mechanism of the synthesis of N-alkyl aniline using glycerol as the reducing agent[21]
Fig. 5 Cu-Au cooperation effect in imine production[22]
Fig. 6 Proposed pathways for the imine formation on P25 TiO2 [24]
Fig. 7 The one-pot synthesis of imine from benzyl alcohol and nitrobenzene on the CdS-TiO2 photocatalyst[25]
Table 2 One-pot synthesis of imines from several benzylic alcohols and nitrobenzene on the CdS-TiO2 photocatalyst[26]
X Time(h) Yields of imines(%)
acetonitrile cyclohexane
H 12 44 99
CF3 24 55 81
Cl 24 59 87
CH3 24 49 81
OCH3 12 70 90
Table 3 Co-N-C/CNT@AC-catalyzed reductive coupling of nitrobenzenes and alcohols to imina [33]
Entry Substrate 1 Substrate 2 Time (h) Conversion
(%)b 		Selectivity
(%)c
1 18 98 99
2 24 98 94
3 28 100 97
4 20 100 90
5 30 98 98
6 36 97 98
7 42 91 97
8 40 95 96
9 36 96 98
10 22 100 99
11 28 75 22
12 24 21 44
13 24 12 10
Fig. 8 A mechanism path for the direct alkylation of nitroarenes[34]
Table 4 Results of the reductive alkylation of nitrobenzenes with alcoholsa [7]
Entry Products t (h) Yield(%)b Entry Products t (h) Yield(%)b
1 12 94 10 24 83
2 12 95
11 24 85
3 12 83 12 18 82
13 24 75
4 12 84
14 24 73
5 12 87
15 12 93
6 12 93
16 12 83
7 12 89
17 24 83
8 16 92
18 12 70
9 24 86
19 24 81
Fig. 9 Proposed mechanism for the reductive N-alkylation of nitro aromatics[35]
Fig. 10 A tentative pathway for the direct alkylation of nitroarenes[38]
Fig. 11 Proposed pathway for secondary amine formation from alcohols and nitroarenes on the photoactivated Pd/TiO2 catalyst[39]
Fig. 12 The reaction mechanism for the reductive amination of nitrobenzene with benzyl alcohol over Co-N-C/CNT@AC[33]
Table 5 Catalytic formation of tertiary amines from nitroarenes and alcohols a[37]
Entry R1 R2 Product Yield(%)c
1 H C6H5 98 (96)
2 p-Me C6H5 94
3 p-MeO C6H5 87
4 p-Cl C6H5 85 (83)
5 m-Me C6H5 88
6 H C6H5CH2 80
7 H p-MeC6H4 92 (90)
8 H p-Cl C6H4 81
9 H o-Cl C6H4 56
10 b H C7H15 70 (67)
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