A growing interest in sulfonyl fluorides in synthetic chemistry stems from their extraordinary thermal and hydrolytic stability and potential as precursors for a myriad of sulfonylated molecules. As a result, current synthetic research has focused on the formation of sulfonyl fluorides using transition metal catalysts. However, the stability of the S—F bond provides a challenge in using sulfonyl fluorides as starting materials in metal-catalyzed reactions. To address this, we have proposed using nickel as a mode to activate sulfonyl fluorides towards their use in cross-coupling reactions. Due to deficient knowledge of this activation mechanism, we have developed a computational protocol—an M06 method with a 6-31+G(d,p)/LanL2DZ basis set—for investigating the thermodynamic energies and kinetic barriers involved in sulfonyl fluoride activation using a bis-imidazolium nickel (0) model system known to successfully activate aryl C–F bonds. Preliminary free energy calculations suggest that both C—S and S—F activation are exergonic reactions. Further investigations into transition states and possible sulfonylated intermediates will hopefully provide us with a theoretical understanding of the catalytic role of nickel in sulfonyl fluoride activation. Applications of this pathway for synthesizing sulfonylated molecules can then be discussed and investigated in detail.

Computational investigation of sulfonyl fluoride activation using bidentate NHC ligands and nickel

255th National Meeting (2018)

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