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[Cu8(μ4-H){S2P(OEt)2}6](PF6): A Novel Catalytic Hydride-Centered Copper Cluster for Azide-Alkyne Cycloaddtion

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Abstract

A hydride-centered dithiophosphate cluster [Cu8(μ4-H){S2P(OEt)2}6](PF6) (1)] previously developed by us was applied as a new catalyst to the 1,3-dipolar cycloaddition of organic azides and alkynes for preparing substituted trizoles. With the required catalyst loading as low as 0.4 mol%, the reactions of terminal alkynes with BnN3 all proceeded smoothly at ambient temperature in CH3CN to exclusively produce 1,4-triazoles in good yields. For these reactions, it is assumed that the formation of the requisite copper acetylide intermediate is facilitated by the abstraction of the terminal hydrogen of alkynes by the hydride released from the central of the cluster. With only few examples being documented in literatures, the reactions of a range of internal alkynes have also been realized under the catalysis of 1 (0.8 mol%) in DMF at elevated temperature, to yield 1,4,5-trisubstituted triazoles in moderate to high yields. Our study has provided a preliminary insight into the effect of sulfur-based ligands on the activity of copper ion.

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Notes

  1. The hydride-donating ability of 1 has recently been realized by its ability to reduce 2-cyclohexenone into cyclohexanone. Treatment of 2-cyclohexenone (10 mg, 0.104 mmol) with 1 (624 mg) in THF (25 mL) at ambient temperature for 12 h resulted in 30 % conversion into cyclohexanone as monitored by gas chromatography

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Acknowledgments

We are grateful to the National Science Council of Republic of China (Taiwan) for financial support.

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Authors and Affiliations

  1. Department of Chemistry, National Dong Hwa University, Hualien, 97401, Taiwan

    Bo-Han Lee, Cheng-Chieh Wu, Xuan Fang, C. W. Liu & Jia-Liang Zhu

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  1. Bo-Han Lee
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  2. Cheng-Chieh Wu
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  3. Xuan Fang
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  4. C. W. Liu
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  5. Jia-Liang Zhu
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Corresponding authors

Correspondence to C. W. Liu or Jia-Liang Zhu.

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Lee, BH., Wu, CC., Fang, X. et al. [Cu8(μ4-H){S2P(OEt)2}6](PF6): A Novel Catalytic Hydride-Centered Copper Cluster for Azide-Alkyne Cycloaddtion. Catal Lett 143, 572–577 (2013). https://doi.org/10.1007/s10562-013-0993-7

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