Noncovalently Functionalized Commodity Polymers as Tailor‐Made Additives for Stereoselective Crystallization

Stereoselective inhibition of the nucleation and crystal growth of one enantiomer aided by “tailor‐made” polymeric additives is an efficient method to obtain enantiopure compounds. However, the conventional preparation of polymeric additives from chiral monomers are laborious and limited in structures, which impedes their rapid optimization and applicability. Herein, we report a “plug‐and‐play” strategy to facilitate synthesis by using commercially available achiral polymers as the platform to attach various chiral small molecules as the recognition side‐chains through non‐covalent interactions. A library of supramolecular polymers made up of two vinyl polymers and six small molecules were applied with seeds in the selective crystallization of seven racemates in different solvents. They showed good to excellent stereoselectivity in yielding crystals with high enantiomeric purities in conglomerates and racemic compound forming systems. This convenient, low‐cost modular synthesis strategy of polymeric additives will allow for high‐efficient, economical resolution of various racemates on different scales. A modular strategy to fabricate “tailor‐made” polymeric additives by attaching chiral small molecules onto achiral commodity polymers through non‐covalent interactions is developed. These supramolecular additives were used in the stereoselective crystallization of various racemates and yielded enantiopure crystals with opposite configurations to the chiral moieties.