Katayev Evgeny A, Boev Nikolay V, Myshkovskaya Ekaterina, Khrustalev Victor N, Ustynyuk Yu A
Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov St., 28, Moscow, 119991 (Russia), Fax: (+7) 499-135-5085.
Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory, 1/3, Moscow, 119991 (Russia).
Chemistry. 2008;14(29):9065-9073. doi: 10.1002/chem.200800860.
The anion-templated syntheses and binding properties of novel macrocyclic oligopyrrole receptors in which pyrrole rings are linked through amide or imine bonds are described. The efficient synthesis was accomplished by anion-templated [1+1] Schiff-base condensation and acylation macrocyclization reactions. Free receptors and their host-guest complexes with hydrochloric acid, acetic acid, tetrabutylammonium chloride, and hydrogen sulfate were analyzed by single-crystal X-ray diffraction analysis. Stability constants with different tetrabutylammonium salts of inorganic acids were determined by standard 1H NMR and UV/Vis titration techniques in [D6]DMSO/0.5% water solution. According to the titration data, receptors containing three pyrrole rings (10 and 12) exhibit high affinity (log Ka=5-7) for bifluoride, acetate, and dihydrogen phosphate, and interact weakly with chloride and hydrogen sulfate. The amido-bipyrrole receptors 11 and 13 with four pyrrole rings exhibit 10(4)- and 10(2)-fold selectivity for dihydrogen phosphate, respectively, as inferred from competitive titrations in the presence of tetrabutylammonium acetate.
本文描述了新型大环低聚吡咯受体的阴离子模板合成及其结合特性，其中吡咯环通过酰胺或亚胺键相连。通过阴离子模板[1+1]席夫碱缩合和酰化大环化反应实现了高效合成。通过单晶X射线衍射分析对游离受体及其与盐酸、乙酸、四丁基氯化铵和硫酸氢盐的主客体配合物进行了分析。在[D6]二甲基亚砜/0.5%水溶液中，采用标准的1H核磁共振和紫外/可见滴定技术测定了与不同无机酸四丁基铵盐的稳定常数。根据滴定数据，含有三个吡咯环的受体（10和12）对双氟化物、乙酸盐和磷酸二氢盐表现出高亲和力（log Ka=5-7），与氯离子和硫酸氢盐的相互作用较弱。从乙酸四丁基铵存在下的竞争滴定推断，具有四个吡咯环的酰胺联吡咯受体11和13对磷酸二氢盐的选择性分别为10(4)和10(2)倍。
