Accurate predictions of C–SO2R bond dissociation enthalpies using density functional theory methods

Abstract

The dissociation of the C–SO₂R bond is frequently involved in organic and bio-organic reactions, and the C–SO₂R bond dissociation enthalpies (BDEs) are potentially important for understanding the related mechanisms. The primary goal of the present study is to provide a reliable calculation method to predict the different C–SO₂R bond dissociation enthalpies (BDEs). Comparing the accuracies of 13 different density functional theory (DFT) methods (such as B3LYP, TPSS, and M05 etc.), and different basis sets (such as 6-31G(d) and 6-311++G(2df,2p)), we found that M06-2X/6-31G(d) gives the best performance in reproducing the various C–S BDEs (and especially the C–SO₂R BDEs). As an example for understanding the mechanisms with the aid of C–SO₂R BDEs, some primary mechanistic studies were carried out on the chemoselective coupling (in the presence of a Cu-catalyst) or desulfinative coupling reactions (in the presence of a Pd-catalyst) between sulfinic acid salts and boryl/sulfinic acid salts.