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Insights into chemoselective fluorination reaction of alkynals via N-heterocyclic carbene and Brønsted base cooperative catalysis

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Abstract

A systematically theoretical study has been carried out to understand the mechanism and chemoselectivity of N-heterocyclic carbene (NHC)-catalyzed fluorination reaction of alkynals using density functional theory calculations. The calculated results reveal that the reaction contains several steps, i.e., formation of the actual catalyst NHC, the nucleophilic attack of NHC on the carbonyl carbon atom of a formyl group, the formation of Breslow intermediate, the removal of methyl carbonate group to afford cumulative allenol intermediate, C–F bond formation coupled with generation of (SO2Ph)2N− anion, esterification accompanied with formation of (SO2Ph)2NH, and dissociation of NHC from product. For the formation of Breslow intermediate via the [1,2]-proton transfer process, apart from the direct proton transfer mechanism, the H2O- and EtOH-mediated proton transfer mechanisms were also investigated, and the free energy barriers for the crucial proton transfer steps can be significantly lowered by explicit inclusion of the protic media EtOH. Furthermore, multiple analyses have also been performed to explore the roles of catalysts and origin of chemoselectivity. Noteworthily, the in situ formed Brønsted base (BB) (SO2Ph)2N− anion was found to play an indispensable role in the esterification process, indicating that the reaction undergoes NHC-BB cooperatively catalytic mechanism, which is remarkably different from the direct esterification pathway proposed in the experimental references. This theoretical work provides a case on the exploration of the dual catalysis in NHC chemistry, which is valuable for rational design on newly cooperative organocatalysis in future.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 21303167), China Postdoctoral Science Foundation (No. 2013M530340 and 2015T80776), and Outstanding Young Talent Research Fund of Zhengzhou University (No.1521316001).

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Authors and Affiliations

  1. College of Chemistry and Molecular Engineering, Center of Computational Chemistry, Zhengzhou University, Zhengzhou, 450001, Henan Province, People’s Republic of China

    Wei Zhang, Yang Wang, Lidong Wang, Zhiyu Wang, Donghui Wei & Mingsheng Tang

  2. Department of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou, 450002, Henan Province, People’s Republic of China

    Yang Wang

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  1. Wei Zhang
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  2. Yang Wang
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  3. Lidong Wang
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  5. Donghui Wei
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  6. Mingsheng Tang
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Correspondence to Donghui Wei.

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Zhang, W., Wang, Y., Wang, L. et al. Insights into chemoselective fluorination reaction of alkynals via N-heterocyclic carbene and Brønsted base cooperative catalysis. Theor Chem Acc 136, 94 (2017). https://doi.org/10.1007/s00214-017-2127-6

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