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“Choose-a-Size” Approach in Dynamic Combinatorial Chemistry: A Single Substrate Dynamic Combinatorial Library of Oligomacrocycles That Adapts to the Size and Shape of Carboxylates

Ulatowski, Filip, Sadowska-Kuziol̷a, Agnieszka, Jurczak, Janusz
Journal of organic chemistry 2014 v.79 no.20 pp. 9762-9770
dimethyl sulfoxide, disulfide bonds, geometry, iodine, models, moieties, nuclear magnetic resonance spectroscopy, organic chemistry, oxidation, thermodynamics, thiols, titration
A neutral anion binding receptor based on dipicolinic acid diamide was equipped with thiol groups in the amidic side arms. After the thiol was oxidized to disulfide groups with I₂, a mixture of cyclic oligomers (a library) was obtained. The distribution of macrocycles can be controlled kinetically during the oxidation process or thermodynamically at basic conditions via disulfide bond exchange. The library proved to be very sensitive to templation with various carboxylates in DMSO. The amplification pattern reflects the structural features of the anionic template and is sensitive to changes in the template’s geometry. The application of carboxylates with multiple functional groups resulted in very strong amplification of the large penta- and hexameric macrocycles. The thermodynamic parameters of some templation effects were rationalized using a simple model and confirmed using competitive NMR titration.