Abstract

Abstract Nanostructures with curved surfaces and chiral‐directing residues are highly desirable in the synthesis of asymmetric chemicals, but they remain challenging to synthesize without using unique templates due to the disfavored torsion energy of twisted architectures toward chiral centers. Here, a strategy for the facile fabrication of highly cured capsule‐shaped catalysts with chiral interiors by the amplification of molecular chirality via the irreversible cross‐linking of 2D asymmetric laminates is presented. The key to the success of these irregular 2D layers is the use of hierarchical assembly of chiral macrocycles, which can exactly regulate the cured nanostructures as well as asymmetric catalysis. The cross‐linking of 2D laminates from the assembly of hexameric macrocycles with one proline edge gave rise to rarely curled capsules with a diameter of 200–400 nm and excellent enantioselectivities as well as diastereoselectivities for asymmetric aldol reactions (94% ee and 1:13 dr). The tetrameric macrocycles decorated with the chiral block produced further curled porous structures, giving an outstanding enantioselectivities (up to 98% ee and 1:17 dr). The strategy of mechanical surface folding will provide a new insight related to increasing the enantioselectivity of chiral organocatalysts.