Diastereoselective Polypseudorotaxane Formation with Planar Chiral Pillar[5]arenes via Co-crystallization Processes

As the number of chiral ring molecules in chiral polyrotaxane increases, the number of possible stereoisomers exponentially increases. Consequently, the selective synthesis of a specific stereoisomer becomes much more challenging. To address this problem, we co-crystallized poly(ethylene glycol) and a diastereomeric ring molecule, pillar[5]arene, in the solid state. The co-crystallization formed polypseudorotaxanes with a high diastereomeric excess (ca. 88 % de), meaning that polypseudorotaxanes containing (S, pS) stereoisomer pillar[5]arene rings were synthesized selectively. By contrast, in solution and evaporation systems, the selectivity remained low (ca. 10 % de). The results suggested that the packing effect by the co-crystallization contributed to the denser assembly of ring molecules on the polymeric chain, resulting in the diastereoselective formation. High diastereoselectivity was also observed even in higher-molecular-weight poly(ethylene glycol)s. These selectivities arose from the cooperative effects of the ring molecules on the polymeric chain, which were supported by calculating the stabilization energy.