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Aerobic Oxidation of Alcohols Catalysed by Cu(I)/NMI/TEMPO System and Its Mechanistic Insights

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Abstract

Homogeneous Cu(I)/NMI/TEMPO catalyst system (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) has been investigated for its catalysis on the aerobic oxidation of 1-octanol and other alcohols into aldehydes under room temperature. The catalytic species was found to be a Cu(I) centre coordinated by two NMI molecules and other two weakly bound solvent molecules, [Cu(NMI)2(Sol)2]+ (Sol = solvent). When CuI was used, this species could be [Cu(NMI)I(Sol)2]. Not like being speculated previously, NMI in this system acts solely as a ligand and its role coordinated to the copper centre enhanced the electron density on the metal centre which promoted the O2 binding in the catalysis. The labile solvent binding to the Cu(I) centre is essential to ensure both oxygen and substrate binding. The catalyst system is suitable for the oxidation of various alcohols using a simple reaction setup and workup. In particular, the system possesses strong oxidizing capability in quantitative conversion of benzylic alcohols regardless of the substituents on the phenyl ring and allylic alcohols into aldehydes. A plausible mechanism was also proposed for the catalysis.

Graphical Abstract

The aerobic oxidation of primary alcohols at room temperature to corresponding aldehydes was achieved by the catalyst composed by Cu(I) and methyl imidazole (NMI) mediated by TEMPO in acetonitrile. The catalytic species is proposed to be such a Cu(I) complex that two of its four coordinating sites are occupied by a strong ligand(s) and the rest two are weakly bound by solvent molecules.

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Acknowledgements

We thank the National Natural Science Foundation of China (Grant No. 21571083), the Natural Science Foundation of Zhejiang Province (Grant No. LY18B010007), China-Australia Institute for Green Materials and Manufacturing Foundation of Jiaxing University (Grant No. 70117012), the Government of Zhejiang Province (Qianjiang Professorship for XL) and Jiaxing University (Summit Program of Jiaxing University for Leading Talents) for supporting this work.

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Authors and Affiliations

  1. School of Chemistry, Nanchang University, Nanchang, 330031, China

    Zhenzhen Liu & Ning Zhang

  2. College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, 314001, China

    Zhongquan Shen, Wei Zhong & Xiaoming Liu

  3. China-Australia Institute for Advanced Materials and Manufacturing, Jiaxing University, Jiaxing, 314001, China

    Zhongquan Shen, Wei Zhong & Xiaoming Liu

Authors
  1. Zhenzhen Liu
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  2. Zhongquan Shen
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  3. Ning Zhang
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  4. Wei Zhong
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  5. Xiaoming Liu
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Correspondence to Wei Zhong or Xiaoming Liu.

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Liu, Z., Shen, Z., Zhang, N. et al. Aerobic Oxidation of Alcohols Catalysed by Cu(I)/NMI/TEMPO System and Its Mechanistic Insights. Catal Lett 148, 2709–2718 (2018). https://doi.org/10.1007/s10562-018-2485-2

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