Intrigued by the catalyst-dependent activity observed in our initial exploration of the reaction space, and driven by the importance of identifying the key catalyst structural features enabling high yields and enantioselectivities, we next sought to apply similar data science tools to understand the structure function relationships imparted by catalyst structure. Molecular descriptors were collected from a single conformer of catalytically active [(Mn V O(OAc)(N4L)] 2+ species, where the lone pair of the carbonyl group of the η 1 -acetate bound ligand holds a weak O•••O interaction with unpaired p electron density of the oxo ligand. Previous studies on iron and manganese catalysts demonstrated that such an interaction energetically stabilizes the active species, and thus enables HAT reactivity. We initially focused on studying the effect of the chiral diamine backbone. For this purpose, different Mn catalysts based on the N,N'-dialkyl-trans-1,2-cyclohexanediamine backbone but differing in the nature of the N-alkyl group were tested in the reaction of S3, and product yields correlated with selected molecular descriptors. Analysis of the %Vbur centered on the oxygen atom of the oxo revealed that as the size of the N-alkyl group increases, the %Vbur gradually increases and correlates well with the observed drop in catalytic turnovers and selectivity (Figure ). As is also evidenced by the optimized geometries, the incorporation of bulky groups in the backbone significantly restricts the accessibility to the Mn=O unit. We anticipated that an expanded data set where the electronic and steric properties of the catalyst are systematically modified would facilitate effective comprehension and prediction of reaction outcomes. To this aim, a data set was therefore constructed by modifying the pyridine moiety of the tetradentate ligand, using the simple chiral pdp (pdp = N,N′bis(2-pyridylmethyl)-2,2′bipyrrolidine), mcp and ecp backbones. S1 was employed as the model substrate using cyclopropanecarboxylic acid as co-catalyst under standard reaction conditions. The screen demonstrates that the yield as well as enantioselectivities are sensitive to the nature of the Mn catalyst, providing enantioselectivities ranging from 24 to 90% (Figure ). Comparatively, catalytic activities using acetic acid follow a similar trend, and the enantioselectivities experience small variations. (2 mol%) using acetonitrile as a solvent and cyclopropanecarboxylic acid as co-ligand at -40 ºC. H2O2 (0.9 M in MeCN, 3.5 equiv.) was delivered over 30 min by syringe pump. Product yields were determined by GC from reaction mixtures using biphenyl as an internal standard. Ee's (in parenthesis) have been determined by GC with chiral stationary phase.