Abstract
<jats:p>Asymmetric catalysis traditionally relies on enantiopure ligands to achieve high enantioselectivity. However, nonlinear effects (NLEs) can enable scalemic catalysts to match or even surpass their enantiopure counterparts. Here, we report an unprecedented phenomenon in zinc-catalyzed alkylation of benzaldehyde using 3,3'-diiodo-BINOL ligand: the enantiopure ligand yields a racemic product, while scalemic versions generate significant enantioselectivity (up to 60% ee). This challenges the paradigm that enantiopure ligands are inherently superior. Mechanistic studies reveal multiple active catalytic species in equilibrium, with distinct enantioselectivities dependent on ligand enantiopurity, catalyst loading, and temperature. Kinetic analyses and VTNA studies confirm non-constant catalyst orders, suggesting higher-order aggregates (e.g., trimers) alongside dimers. This work demonstrates how scalemic ligands can outperform enantiopure ones, offering a new perspective on chiral amplification and practical advantages in catalytic design.</jats:p>