Aggregation‐Induced Enantioselective Michael Addition of 1,3‐Dicarbonyls to β‐Nitroalkenes

H-NMR investigations directly link aggregate structures to catalytic microsteps. Mechanistic studies uncover a distinct catalytic pathway that departs from classical homogeneous catalysis, featuring catalyst aggregation, aggregation-induced substrate activation, co-assembly, and reversible dissociation during turnover. This work establishes aggregation as a fundamental mechanistic motif in asymmetric organocatalysis and provides a unified framework for the rational design of aggregation-induced catalytic systems.