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

Danyi Chen; Yanmei Zhou; Haifeng Zhou; Sensheng Liu; Qixing Liu; Kaili Zhang; Yasuhiro Uozumi

doi:10.1055/s-0037-1610086

Synlett, Inhaltsverzeichnis

Synlett 2018; 29(13): 1765-1768
DOI: 10.1055/s-0037-1610086

letter

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

Danyi Chen

^aResearch 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

^aResearch 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

,

Haifeng Zhou *

^aResearch 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

^aResearch 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

^aResearch 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

^aResearch 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*

^aResearch 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

^bInstitute for Molecular Science (IMS), Myodaiji, Okazaki 444-8787, Japan eMail: uo@ims.ac.jp

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Abstract

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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.

Key words

diboronic acid - nitro aromatics - amines - reduction - water

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Referenzen

References and Notes

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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.

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