Next, we sought to gain additional insights into the features of the novel oxazoline preligands. The fundamental understanding of the ligand's structural and electronic modularity provides reasonable mechanistic insights, efficient ligand tuning with wide applicability, and reaction optimizations. Thus, a comprehensive theoretical parameterization study was performed to develop a quantitative structure-activity relationship (QSPR) model for the ligands (see Supporting Information for details). Several DFTbased descriptors were obtained from the optimized free preligand (FL) structures and cyclometalated cobalt(III)complexes (CMC) (Figure ). Thus, the properties of the isolated preligand and the complex formed were taken into consideration. All possible combination-based multi-variant linear regression (MVLR) models were constructed and tested up to 6 parameters. From the performance evaluation, the four-parameter-based model (M4) gave satisfactory selectivity predictions for both (Figure ) train (R2 score = 0.81, MAE = 0.16 kcal mol -1 ) and test (R2 score = 0.75, MAE = 0.26 kcal mol -1 ) samples. Additionally, the model also performed well (MAE = 0.20 kcal mol -1 ) during the leave-one-out (LOO) train sample cross-validation, which demonstrated a robust and good generalization ability towards both samples. Notably, the four-parameterbased M4 model comprised of sterimol component at the C2 substituent (s_C2_L), the natural bonding orbital (NBO) charges at C2 and C6 (nbo_C2, nbo_C6), and the probed interaction energy (IE) between the ligand as well as the substrate. The model suggested a significant role of nbo_C6 and IE parameters of C6 substituents in stabilizing the substrate plane, while the C2 site of the ligand demanded lower electron density to induce better selectivity for the given reaction (Figure ). For a given reaction, the trade-offs between a ligand's selectivity and reactivity play a critical role. Thus, to further evaluate the contributing features obtained from the M4 model, we performed a feature-wise univariate reactivity (yield) classification to identify the feature thresholds for higher ligand reactivity (Figure ) (see Supporting Information for details). The classification identified 6.42 Å as the maximum threshold for s_C2_L, suggesting that substitutions above this threshold would result in lower yields. For the IE a minimum threshold of -0.421 kcal mol -1 (stabilizing interaction) was obtained. Interestingly, a pattern was observed in the substituents at C6: all the alkyl substituents located in the region, where IE > -0.421 kcal mol -1 , presented lower yields. In contrast, phenyl-substituted oxazoline ligands, which occurred in the opposite region, presented higher yields. The ligand L8, with the highest stabilizing interaction energy, conferred the highest yield. The obtained maximum thresholds for nbo_C6 and nbo_C2 were -0.07 and 0.57, respectively. The nbo_C2 was classified most accurately, revealing that ligands with an NBO charge at the C2 carbon higher than 0.57 will provide low yields, where the entire tested amide ligand class was present. Thus, based on the developed final model; the nbo_C2_CMC, nbo_C6_CMC, s_C2_L_FL, and IE_CMC are the most important features from the ligand determining the stereoselectivity. Moreover, the nbo_C2_CMC and IE_CMC were also found to better predict the reactivity thresholds of the ligand. With the identified selectivity model and the obtained threshold values, virtual screening of the ligand classes can be efficient in determining ligands with higher selectivity as well as reactivity. Subsequently, we focused on evaluating the viable substrate scope of the desired transformation (Figure ). First, different substitutions on the aromatic ring of the hydrazone were examined (5-19). Sensitive halogen functionalities (6-8), ether (9), thioether (10), carboxylate ester (11), and acetamido (12) moieties were tolerated under the reaction conditions, furnishing the desired products in synthetically useful yields and high e.r. Alkyl substituents at different positions of the aromatic ring delivered the desired annulated products (13-17) with good yield and high enantioselectivity (up to 97.0:3.0 e.r.). Sterically hindered hydrazone analogues furnished the annulated products (18-19) at the sterically less hindered site. Second, alkyl substituents on the hydrazone were examined. Alkyl groups of various lengths (20-24) and a cyclopropyl moiety (25) were accommodable, gaining access to corresponding products with high selectivity. The presence of an ether moiety in the aliphatic chain (24) was also suitable for this transformation. In all the cases, very high diastereoselectivities could be achieved (up to >20:1).