Citation: Yibing Wang, Xiaoning Guo, Manqian Lü, Zhaoyang Zhai, Yingyong Wang, Xiangyun Guo. Cu₂O/SiC as efficient catalyst for Ullmann coupling of phenols with aryl halides[J]. Chinese Journal of Catalysis, ;2017, 38(4): 658-664. doi: 10.1016/S1872-2067(17)62785-2 shu

Cu₂O/SiC as efficient catalyst for Ullmann coupling of phenols with aryl halides

a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China

Received Date: 24 November 2016
Revised Date: 2 January 2017

Fund Project: This work was supported by the National Natural Science Foundation of China (21203233, 21473232, 21403270) and Youth Innovation Promotion Association, CAS (2013115).

ACu₂O/SiC heterogeneous catalyst was prepared via a two-step liquid-phase method using diethylene glycol as both the solvent and the reducing agent. The catalyst was characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and H₂ temperature-programmed reduction. All the results indicate that Cu is present on the SiC support primarily as Cu₂O. The SEM and TEM results show that cubic Cu₂O nanoparticles are uniformly dispersed on the β-SiC surface. The reaction conditions, namely the temperature, reaction time, and amounts of base and catalyst used, for the Ullmann-type C-O cross-coupling reaction were optimized. A model reaction was performed using iodobenzene (14.0 mmol) and phenol (14.0 mmol) with Cu₂O/SiC (5 wt% Cu) as the catalyst, Cs₂CO₃ (1.0 equiv.) as the base, and tetrahydrofuran as the solvent at 150℃ for 3 h; a yield of 97% was obtained and the turnover frequency (TOF) was 1136 h^-1. The Cu₂O/SiC catalyst has a broad substrate scope and can be used in Ullmann-type C-O cross-coupling reactions of aryl halides and phenols bearing a variety of different substituents. The catalyst also showed high activity in the Ullmann-type C-S cross-coupling of thiophenol with iodobenzene and substituted iodobenzenes; a TOF of 1186 h^-1 was achieved. The recyclability of the Cu₂O/SiC catalyst in the O-arylation of phenol with iodobenzene was investigated under the optimum conditions. The yield decreased from 97% to 64% after five cycles. The main reason for the decrease in the catalyst activity is loss of the active component, i.e., Cu₂O.
- Cuprous oxide,
- Silica carbide,
- Ullmann coupling,
- O-arylation,
- Phenols,
- Aryl halide
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Cu₂O/SiC as efficient catalyst for Ullmann coupling of phenols with aryl halides