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Complementary Base Lowers the Barrier in SuFEx Click Chemistry for Primary Amine Nucleophiles

preprint
submitted on 02.10.2020 and posted on 05.10.2020 by Jan-Niclas Luy, Ralf Tonner
The Sulfur (VI) Fluoride Exchange (SuFEx) reaction is an emerging scheme for connecting molecular building blocks. Due to its broad functional group tolerance and rather stable resulting linkage it is seeing rapid adoption in various fields of chemistry. Still, to date the reaction mechanism is poorly understood which hampers further development. Here, we show that the mechanism of the SuFEx reaction for the prototypical example of methanesulfonyl fluoride reacting with methylamine can be understood as an SN2-type reaction. By analyzing the reaction path with the help of density functional theory in vacuo and under consideration of solvent and co-reactant influence we identify the often used complementary base as crucial ingredient to lower the reaction barrier significantly by increasing the nucleophilicity of the primary amine. With the help of energy decomposition analysis (EDA) at the transition state structures we quantify the underlying stereo-electronic effects and propose new avenues for experimental exploration of the potential of SuFEx chemistry.

Funding

SFB 1083:  Structure and Dynamics of Internal Interfaces

Deutsche Forschungsgemeinschaft

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History

Email Address of Submitting Author

jan-niclas.luy@uni-leipzig.de

Institution

Universität Regensburg

Country

Germany

ORCID For Submitting Author

0000-0002-0552-5223

Declaration of Conflict of Interest

The authors declare that there is no conflict of interest.

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