An extensive experimental and computational analysis of this cinchona-phosphinate catalyzed chemospecific acylation of sulfonimidamides was conducted. A data science-informed substrate and catalyst scope evaluation allowed for statistical modeling to inform traditional physical organic mechanistic studies including reaction kinetics, catalyst structural studies, and DFT transition state analysis. The catalyst "active site" was mapped by deconstructing the important model parameters in conjunction with insight from these traditional physical organic techniques. We have developed a comprehensive understanding of the catalyst-substrate structure-activity relationship that accounts for the selectivity of this reaction. Ultimately, the enantioselectivity determining event was proposed to be the collapse of the tetrahedral intermediate, which is often hypothesized for enzymatic processes, not small molecule catalysis. This should provide inspiration for the development of related reactions involving the use of chiral sulfur (VI) pharmacophores. Additionally, this study highlights how data science tools can be merged with traditional physical organic methods in the pursuit of mechanistic analysis.