Enantioselective Nickel‐Catalyzed Hydrogenation of α‐Alkylidene Succinimides Enabled by Weak Noncovalent Interactions

The development of asymmetric hydrogenation catalysts based on Earth‐abundant metals presents a sustainable alternative to efficient but resource‐limited rare‐metal systems. However, these catalysts often suffer from low catalytic activity. In this study, through a combination of density functional theory (DFT) calculations and kinetic experiments, we uncovered a positive correlation between catalyst‐substrate weak noncovalent interactions and catalytic efficiency in the enantioselective nickel‐catalyzed hydrogenation of α‐alkylidene succinimides with different N‐protecting groups. The tert‐butyl (tBu) substituent emerged as the optimal choice, significantly enhancing reactivity. This approach enabled the hydrogenation of a wide range of substrates with excellent yields (up to 99%) and enantioselectivities (up to 99% ee), achieving a substrate/catalyst (S/C) ratio of 4000—twice the efficiency of rare‐metal catalysts (S/C ≤ 2000) for similar transformations. Energy decomposition analysis (EDA) of the enantiomers revealed that the high stereoselectivity is promoted by stabilizing weak noncovalent interactions in the R‐configured transition state.