Topology of Gemini‐shaped Hexagonal Heterojunction for Efficient Stereoconvergent Transformation via Dynamic Kinetic Resolution

Abstract Despite recent advances in the combination of kinetic resolution and racemization for efficient stereoconvergent transformation, the poor stability and limited reaction activities of the products restrict their wide application in industrial production. To overcome these problems, Gemini‐shaped hexagons with para‐heterojunctions for one‐dimensional and two‐dimensional supramolecular polymers were designed via hydrogen‐bonding adhesion by racemization catalyst 1 and kinetic resolution 2 in this work. The polymers from the assembly of Gemini‐shaped hexagons exhibit rapid catalytic behaviour with efficient selectivity for the desired configuration in the synthesis of tertiary alcohols with contiguous stereocenters through dynamic kinetic resolution for the nanoscale heterojunctions of dissimilar catalysts. Among them, the developed 2D polymers gave outstanding enantioselectivities and diastereoselectivities (>99 % ee, 20 : 1 dr) through the cooperation of adjacent dissimilar catalysts. The heterojunctions varying dimensions and distances of dissimilar catalysts provide new insight for increasing the enantioselectivity of chiral organocatalysts.