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Theoretical modeling of homogenous gold-catalyzed or NaH-supported alkyne cyclization

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Abstract

Gold-catalyzed or NaH-supported formation mechanisms of pyrazine and diazepines were investigated computationally. The structural properties of these heterocyclic compounds were studied in the gas phase and various solvents. Density functional theory, including B3LYP, WB97X-D, M06-2X, and M06 hybrid functional methods, was used to locate and discuss the energetics of the intermediates and the transition states. The nature of the substituents attached to the terminal alkyne played an essential role in these mechanisms. Electron-donating or electron-withdrawing substituents indicated in which direction the cyclization would evolve. Natural bond orbital analysis was performed to determine the chemoselectivity of the products.

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Acknowledgements

Financial support from the Scientific Research Department (BAP, Project No. FEF.19001.19.003) of Hitit University is gratefully acknowledged. Thanks are also due to the Scientific and Technological Research Council of Turkey (TUBITAK) to use its ULAKBIM/TRUBA high performance and grid computing centre.

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  1. Department of Chemistry, Hitit University, 19030, Çorum, Turkey

    Sinan Basceken

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  1. Sinan Basceken
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Correspondence to Sinan Basceken.

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Basceken, S. Theoretical modeling of homogenous gold-catalyzed or NaH-supported alkyne cyclization. Monatsh Chem 152, 607–624 (2021). https://doi.org/10.1007/s00706-021-02775-x

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