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Highly efficient NHC-iridium-catalyzed β-methylation of alcohols with methanol at low catalyst loadings

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Abstract

The methylation of alcohols is of great importance since a broad number of bioactive and pharmaceutical alcohols contain methyl groups. Here, a highly efficient β-methylation of primary and secondary alcohols with methanol has been achieved by using bis-N-heterocyclic carbene iridium (bis-NHC-Ir) complexes. Broad substrate scope and up to quantitative yields were achieved at low catalyst loadings with only hydrogen and water as by-products. The protocol was readily extended to the β-alkylation of alcohols with several primary alcohols. Control experiments, along with DFT calculations and crystallographic studies, revealed that the ligand effect is critical to their excellent catalytic performance, shedding light on more challenging Guerbet reactions with simple alcohols.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2016YFA0202902), the National Natural Science Foundation of China (21871059, 21861132002) and the Department of Chemistry at Fudan University.

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Authors and Affiliations

  1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai, 200438, China

    Zeye Lu, Qingshu Zheng, Guangkuo Zeng, Yunyan Kuang & Tao Tu

  2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China

    Tao Tu

  3. Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China

    Tao Tu

  4. Green Chemistry Centre of Excellence, University of York, York, YO 105DD, UK

    James H. Clark

Authors
  1. Zeye Lu
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  2. Qingshu Zheng
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  3. Guangkuo Zeng
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  4. Yunyan Kuang
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  5. James H. Clark
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  6. Tao Tu
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Correspondence to Tao Tu.

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Conflict of interest The authors declare no conflict of interest.

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Lu, Z., Zheng, Q., Zeng, G. et al. Highly efficient NHC-iridium-catalyzed β-methylation of alcohols with methanol at low catalyst loadings. Sci. China Chem. 64, 1361–1366 (2021). https://doi.org/10.1007/s11426-021-1017-0

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  • DOI: https://doi.org/10.1007/s11426-021-1017-0

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