TY - JOUR

T1 - Synthesis and spectroscopic studies of triazole-based macroheterocycles containing eudesmane-type sesquiterpenoid moieties

AU - Patrushev, Sergey S.

AU - Vasil'eva, Daria O.

AU - Krasnov, Vyacheslav I.

AU - Rybalova, Tatyana V.

AU - Nefedov, Andrey A.

AU - Shults, Elvira E.

N1 - Сведения о финансировании Финансирующий спонсор Номер финансирования Акроним Russian Science Foundation 23-73-00077 RSF

PY - 2025/2/5

Y1 - 2025/2/5

N2 - 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.

AB - 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.

KW - 1,2,3-triazoles

KW - X-ray structure

KW - azide-alkyne cycloaddition

KW - isoalantolactone

KW - macroheterocycles

UR - https://www.mendeley.com/catalogue/17372a80-bb93-3752-be2e-c6a1d2364631/

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85205296149&origin=inward&txGid=ec3a120842956ea440cd885bebd4164a

U2 - 10.1016/j.molstruc.2024.140236

DO - 10.1016/j.molstruc.2024.140236

M3 - Article

VL - 1321

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

M1 - 140236

ER -