Weak Attractive Noncovalent Interactions in Metal‐Catalyzed Asymmetric Hydrogenation

Abstract Weak attractive noncovalent interactions, specifically CH/π⋯HC/π and CH⋯O/N contacts, between catalysts and substrates have recently gained renewed attention in asymmetric hydrogenations, despite their historical underappreciation due to challenges in detection. Emerging evidence underscores the significant role of these interactions in improving reactivity and/or enantioselectivity, particularly in sustainable catalytic systems that utilize Earth‐abundant transition metals. This minireview summarizes advancements in asymmetric hydrogenations catalyzed by both noble and Earth‐abundant metal complexes under an H₂ atmosphere, with a focus on the roles of CH/π⋯HC/π and CH⋯O/N noncovalent interactions in improving reactivity and/or enantioselectivity. Taking into account the weak attractive character of these noncovalent interactions, it is expected to help the design of novel chiral transition metal catalysts and develop more efficient asymmetric hydrogenation systems for the large‐scale synthesis of diverse chiral compounds.