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Mechanism of the palladium-catalyzed hydrothiolation of alkynes to thioethers: a DFT study

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Abstract

The mechanisms of the palladium-catalyzed hydrothiolation of alkynes with thiols were investigated using density functional theory at the B3LYP/6-31G(d, p) (SDD for Pd) level. Solvent effects on these reactions were explored using the polarizable continuum model (PCM) for the solvent tetrahydrofuran (THF). Markovnikov-type vinyl sulfides or cis-configured anti-Markovnikov-type products were formed by three possible pathways. Our calculation results suggested the following: (1) the first step of the cycle is a proton-transfer process from thiols onto the palladium atom to form a palladium-thiolate intermediate. The palladium-thiolate species is attacked on alkynes to obtain an elimination product, liberating the catalyst. (2) The higher activation energies for the alkyne into the palladium–thiolate bond indicate that this step is the rate-determining step. The Markovnikov-type vinyl sulfide product is favored. However, for the aromatic alkyne, the cis-configured anti-Markovnikov-type product is favored. (3) The activation energy would reduce when thiols are substituted with an aromatic group. Our calculated results are consistent with the experimental observations of Frech and colleagues for the palladium-catalyzed hydrothiolation of alkynes to thiols.

Density functional theory calculations on the mechanisms of the palladium-catalyzed hydrothiolation of aliphatic and aromatic alkynes with aliphatic and aromatic thiols suggest three pathways leading to the formation of Markovnikov-type vinyl sulfides or cis-configured anti-Markovnikov-type products

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Acknowledgments

This work was supported by Lanzhou University of Arts and Science Research and innovation team of new chemical materials. We are grateful to the Gansu Province Supercomputer Center for essential support.

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Authors and Affiliations

  1. College of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, Gansu, 730010, People’s Republic of China

    Xing-hui Zhang, Ke-tai Wang & Shan-shan Li

  2. Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Key Laboratory of Eco-environment-related Polymer Materials, Ministry of Education, Northwest Normal University, Lanzhou, Gansu, 730070, People’s Republic of China

    Zhi-yuan Geng

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  1. Xing-hui Zhang
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Correspondence to Xing-hui Zhang.

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Supporting Information

Text giving the complete citation for [57], tables giving Cartesian coordinates for the calculated stationary structures and the sum of the electronic and zero-point energies for the transition and ground states obtained from the DFT calculations. (DOC 560 kb)

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Zhang, Xh., Geng, Zy., Wang, Kt. et al. Mechanism of the palladium-catalyzed hydrothiolation of alkynes to thioethers: a DFT study. J Mol Model 20, 2409 (2014). https://doi.org/10.1007/s00894-014-2409-z

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