Enzyme‐Analogue Built Polymers XII Specific Binding Effects in Chiral Microcavities of Crosslinked Polymers

Abstract 2,3‐O‐(4‐Vinylphenylboronic)esters (2a–c) of different D‐glyceric esters were copolymerized to macroporous, crosslinked polymers. After the glyceric esters 1a–c, acting as templates, had been split off, chiral microcavities with one boronic acid group per cavity were formed. These polymers were capable of resolving the racemate of the template used. By comparison of resolution‐specificities of polymers prepared from glyceric esters carrying different bulky groups in the ester moiety, the influence of the size of substituents at the asymmetric C could be determined. The polymers showed the most specific racemic resolution for the racemate of the template used. Small differences between the structure of the racemate and that of the template used led to a decrease of specificity; bigger differences resulted in a complete disappearence of specificity. Furthermore, it was investigated whether non‐covalent interactions between the template and added comonomers were strong enough during polymerization to allow the formation of specific structures within the cavities. The directed introduction of charge‐transfer interaction led to a strong increase in specificity for racemic resolution.