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Reaction mechanism of organoselenium-catalyzed syn-dichlorination of alkenes: a DFT study

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Abstract

A new method for the syn-dichlorination of alkenes at room temperature has been proposed by Denmark et al. The method uses diselenide (PhSeSePh) as the precatalyst, benzyltriethylammonium chloride (BnEt3NCl) as the source of chlorine, and an N-fluoropyridinium salt as the oxidant to recover the catalyst. This approach has achieved exquisite diastereocontrol on a number of alkene substrates. In this paper, we report the results of DFT calculations we performed to study the mechanism of this reaction. We were able to identify a reasonable reaction path, including the intermediate and transition-state structures. The results also indicate that PhSeCl3, rather than PhSeCl, is the active catalyst.

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Acknowledgments

We would like to thank the National Natural Science Foundation for financial support.

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Authors and Affiliations

  1. Institute of Theoretical Chemistry, School of Chemistry and Chemical Engineering and Key Laboratory of Colloid and Interface Chemistry (Ministry of Education), Shandong University, Jinan, Shandong, 250100, People’s Republic of China

    Lijun Fu, Xueli Mu & Baiqing Li

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  1. Lijun Fu
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  2. Xueli Mu
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  3. Baiqing Li
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Correspondence to Baiqing Li.

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Fu, L., Mu, X. & Li, B. Reaction mechanism of organoselenium-catalyzed syn-dichlorination of alkenes: a DFT study. J Mol Model 24, 91 (2018). https://doi.org/10.1007/s00894-018-3624-9

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