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DFT insight into Hashmi phenol synthesis catalyzed by Au single-walled nanotubes: mechanism and charge effect

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Abstract

The mechanism and charge effect of cycloisomerization of ω-alkynylfuran (Hashmi phenol synthesis) catalyzed by single-walled helical gold nanotubes (Au SWNTs) have been systematically investigated via density functional theory. Cycloisomerization of ω-alkynylfuran occurs by the 5-exo Friedel–Crafts-type (FCT) mechanism, namely 5-exo cyclization, furan ring opening, and ring closing of the dienone carbene–gold intermediate. The reactions with Au(6,0), Au(6,1), Au(6,2) and Au(6,3) SWNTs show low energy barriers along the 5-exo FCT path in acetonitrile solvent, but have different the rate-determining steps. From an energy perspective, the reaction rate-determining step catalyzed by Au(6,0) and Au(6,3) is the ring-closing of dienone carbine-gold intermediate, but that of Au(6,1) and Au(6,2) is the IM5 dissociation from the Au SWNTs, which can be attributed to the diversity of the d-band centers of the Au(6,m) SWNTs. The effect of the charge of the Au SWNTs on the catalytic activity was also investigated. Theoretical analysis shows a prominent charge effect, where the cationic Au(6,0), Au(6,3) SWNTs and anionic Au(6,1), Au(6,2) SWNTs are more favorable for the Hashmi phenol synthesis reaction. This results can be attributed to the Au(6,0) and Au(6,3) SWNTs with positive charge can reduce the adsorption energy of the substrate on the catalyst surface and decrease the energy barrier of the cyclization process and ring-closing step. Besides, the Au(6,1) and Au(6,2) with an anion could obviously decrease the dissociation energy of IM5 which is help for the Hashmi phenol reaction. Theoretical analysis shows that the structure and charge effects could influence the catalytic activity of Au(6,m) SWNTs toward Hashmi phenol synthesis. This work will provide insight into cycloisomerization of ω-alkynylfuran and valuable information for application of Au SWNTs in catalysis.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 21573030), National Key Research and Development Program of China (2018YFC1602101), National Key Research, the Chongqing Science and Technology Commission, China (Grant No. CSTC2018JCYJAX0041) and Project of Chongqing Key Laboratory of Environmental Materials and Restoration Technology (CEK1803).

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Authors and Affiliations

  1. National and Local Joint Engineering Research Center of Targeted and Innovative Therapeutics, Chongqing Key Laboratory of Kinase Modulators As Innovative Medicine, Chongqing Collaborative Innovation Center of Targeted and Innovative Therapeutics, College of Pharmacy and International Academy of Targeted Therapeutics and Innovation, Chongqing University of Arts and Sciences, Chongqing, 402160, People’s Republic of China

    Xiao Yan, Yafei Luo, Zhongzhu Chen, Zhigang Xu & Dianyong Tang

  2. College of Pharmacy and Biological Engineering, Key Laboratory of Medicinal and Edible Plants Resources Development of Sichuan Education Department, Sichuan Industrial Institute of Antibiotics, Chengdu University, Chengdu, 610106, People’s Republic of China

    Xiao Yan, Hailian Yan, Qing Luo, Gang Zhao & Jianping Hu

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  1. Xiao Yan
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Correspondence to Dianyong Tang, Gang Zhao or Jianping Hu.

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Yan, X., Luo, Y., Yan, H. et al. DFT insight into Hashmi phenol synthesis catalyzed by Au single-walled nanotubes: mechanism and charge effect. Theor Chem Acc 140, 12 (2021). https://doi.org/10.1007/s00214-020-02715-8

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