Synlett 2018; 29(13): 1765-1768
DOI: 10.1055/s-0037-1610086
letter
© Georg Thieme Verlag Stuttgart · New York

Metal-free Reduction of Nitro Aromatics to Amines with B2(OH)4/H2O

Danyi Chen
a   Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, P. R. of China   Email: zhouhf@ctgu.edu.cn
,
Yanmei Zhou
a   Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, P. R. of China   Email: zhouhf@ctgu.edu.cn
,
a   Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, P. R. of China   Email: zhouhf@ctgu.edu.cn
,
Sensheng Liu
a   Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, P. R. of China   Email: zhouhf@ctgu.edu.cn
,
Qixing Liu
a   Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, P. R. of China   Email: zhouhf@ctgu.edu.cn
,
Kaili Zhang
a   Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, P. R. of China   Email: zhouhf@ctgu.edu.cn
,
Yasuhiro Uozumi*
a   Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, P. R. of China   Email: zhouhf@ctgu.edu.cn
b   Institute for Molecular Science (IMS), Myodaiji, Okazaki 444-8787, Japan   Email: uo@ims.ac.jp
› Author Affiliations
National Natural Science Foundation of China (21202092). Startup Foundation from the China Three Gorges University (KJ2012B080, KJ2014H008).
Further Information

Publication History

Received: 10 May 2018

Accepted after revision: 13.05,2018

Publication Date:
19 June 2018 (online)


Abstract

A metal-free reduction of nitro aromatics mediated by di­boronic acid with water as both the hydrogen donor and solvent under mild conditions has been developed. A series of aromatic amines were obtained with good functional group tolerance and in good yields.

Supporting Information

 
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  • 15 Aniline (2a) Nitrobenzene (123 mg, 1.0 mmol), B2(OH)4 (448 mg, 5.0 mmol, 5.0 equiv), and H2O (3.0 mL) were added to a 10 mL tube. The reaction mixture was stirred at 80 °C for 8 h. When the reaction was complete (monitored by TLC), the mixture was cooled to r.t. and extracted with ethyl acetate (3 × 20 mL). The combined organic phase was dried with anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography. Colorless oil (92 mg, 99%); 1H NMR (400 MHz, CDCl3): δ = 7.27–7.22 (m, 2 H), 6.87–6.83 (m, 1 H), 6.76 (dd, J1 = 7.6 Hz, J2 = 0.8 Hz, 2 H), 3.66 (br, 2 H) ppm; 13C NMR (101 MHz, CDCl3): δ = 146.60, 129.49, 118.72, 115.30 ppm.