В журнале Journal of Molecular Structure (IF 4) опубликована статья сотрудников Института: к.х.н. С.С. Патрушева (снс, ЛМХ), Д.О. Васильевой, к.х.н. В.И. Краснова (снс ГЯМР), Т.В. Рыбаловой (нс, ГРСА), к.х.н. А.А. Нефедова (снс, рук. группы ГМС) и.д.х.н., проф. Э.Э. Шульц (гнс, ЛМХ):
Synthesis and spectroscopic studies of triazole-based macroheterocycles containing eudesmane-type sesquiterpenoid moieties
Sergey S. Patrushev, Daria O. Vasil'eva, Vyacheslav I. Krasnov ,Tatyana V. Rybalova, Andrey A. Nefedov, Elvira E. Shults
Journal of Molecular Structure, V. 1321, Part 5, 5 February 2025, 140236
DOI: 10.1016/j.molstruc.2024.140236
Highlights
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Chiral macrocyclic compounds with a natural eudesmane type methylene lactone as a structural motif.
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Synthesis of chiral macroheterocyclic compounds via azide-alkyne cycloaddition.
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Study of Zn(II) and Mg(II) ion complexation of macrocycles using NMR titration method.
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Structure of new type of hybrid compounds was established by X-ray crystallography.
Abstract
Chiral recognition is one of the most important and fascinating areas in supramolecular chemistry. Chiral macrocycles, especially chiral macrocyclic hosts, having stable structures, adjustable internal cavities to encapsulate and complexation have been developed during the last decade. Attention has been paid on the synthesis of covalently linked of rigid units on the side chain of macrocycles with active binding motifs. In this study, new synthetic protocols has been developed for preparation of optically active triazole-based macrocyclic compounds in which eudesmane-type sesquiterpene lactones act as pendent moieties by the implementation of the copper(I)-catalyzed azid-alkyne cycloaddition strategies. The described protocols provided mild reaction conditions, high yields and high atom- and step-economy. New macrocycles with hanging dihydroisoalantolactone units, different combinations of heteroatoms, and ring sizes in the range of 16–36 atoms were characterized by NMR and UV–vis spectroscopy and mass spectrometry analysis. The molecular structures and intermolecular interactions of two new macrocyclic compounds were elucidated using single-crystal X-ray crystallography. Upon addition of Mg(II) or Zn(II) cations to these novel ligands, using titration experiments we observed the formation of 1:1 (16:Mg2+) complexes and 1:1 to 2:1 (16:Zn2+) complexes, respectively, according to stoichiometry. The result suggests that dihydriisoalantolactone and triazole units within the molecules formed complexes with Mg (II) and Zn (II) ions in solution.