This paper uses the phosphine oxazoline ligands 1 and an allylation transformation (reaction 1) to illustrate the value of divergent ligand syntheses and high-throughput screening in catalyst discovery and optimization. Thus, a diverse set of ligands 1 (Table 1) was prepared via a divergent synthesis involving the pivotal intermediate, phosphine-substituted amino alcohol 7 (Scheme 1). Single-crystal X-ray crystallographic data was obtained for a nickel complex 8 (Figure 3) of the phenyl-substituted ligand 1i. This analysis illustrated some structural features of the ligand systems 1 that may be conducive to asymmetric catalysis. High-throughput screens were then used to correlate the ligand 1 R-substituents with asymmetric induction in the allylation reaction 1, and it emerged that the pseudo-spherical adamantyl substituent was superior to other R-substituents. Other parameters in the catalyst systems were also varied, sometimes in “two-dimensional” screens. No pronounced solvent effects were identified. ...