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A mechanistic investigation of metal-free allylic fluorination of styrenes for the synthesis of allyl fluoride derivatives using density functional theory

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Abstract

The primary objective of this work is to delve into the intricacies of allylic fluorination reactions through the application of density functional theory (DFT) calculations. These reactions hold significant importance in the realm of synthesizing organofluorine compounds. The specific focus lies on comprehending the interaction mechanisms when styrenes, a class of organic molecules, come in contact with an electrophilic fluorinating reagent known as Selectfluor. Notably, this interaction pathway demonstrates remarkable efficiency in yielding allylic fluoride products. The proposed mechanism for this transformation involves a sequential process. To unveil the microcosmic intricacies governing this reaction between the alkene substrate and Selectfluor, advanced computational methodologies are employed. The paper systematically outlines the computational strategies harnessed to probe the minute details of the reaction mechanism. The outcomes of these computations are subsequently subjected to thorough analysis, encompassing crucial facets such as transition states and energy barriers. This analytical depth enhances the fundamental understanding of the reaction mechanism and sheds light on the underlying factors influencing its feasibility and efficiency. In a broader context, the insights garnered from this study carry significant utility. They provide pivotal guidance for the optimization of reaction conditions, facilitating the fine-tuning of experimental setups. Moreover, the elucidated mechanism serves as a platform for the design of even more efficient and selective allylic fluorination reactions. This paper, by amalgamating theoretical insights with practical synthetic objectives, contributes to the broader advancement of organofluorine compound synthesis and allied fields.

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Acknowledgements

Useful resources from the Department of Chemistry, Panjab University, are sincerely acknowledged.

Funding

This work was supported by Department of Science and Technology, Ministry of Science and Technology, India (Grant number – [DST/INSPIRE/04/2017/002529]).

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Authors and Affiliations

  1. P.G. Department of Chemistry, Multani Mal Modi College, Patiala, 147001, Punjab, India

    Harjinder Singh

  2. Department of Chemistry & Centre for Advanced Studies in Chemistry, Panjab University, Chandigarh, 160014, India

    Vaneet Saini

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Contributions

V. S.: conceptualization, methodology, software, supervision, writing—original draft, reviewing and editing, validation, visualization, project administration, resources H. S.: software, data curation, software, writing- original draft, reviewing and editing, validation, visualization, resources.

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Correspondence to Vaneet Saini.

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Singh, H., Saini, V. A mechanistic investigation of metal-free allylic fluorination of styrenes for the synthesis of allyl fluoride derivatives using density functional theory. Struct Chem (2023). https://doi.org/10.1007/s11224-023-02253-6

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