Trybrat O. Synthesis and properties of functionalized inherently chiral calix[4]arenes.

Українська версія

Thesis for the degree of Doctor of Philosophy (PhD)

State registration number

0825U000001

Thesis Registration Form

0825U000001.pdf

Applicant for

Specialization

  • 102 - Хімія

10-01-2023

Specialized Academic Board

47679

Institute of Organic Chemistry NAS of Ukraine

Essay

The thesis is devoted to the development of methods for the synthesis of new inherently chiral calix[4]arene derivatives with different functional groups on the lower and upper rims, as well as the study of their enantio-binding properties. The topic of the thesis project is relevant in view of the significant potential of using chiral calixarenes as enantioselective sensors and sorbents for chiral chromatography. Methods of sequential regioselective alkylation of OH groups of hydroxycalix[4]arenes were developed and, using chiral auxiliary groups, new enantiomerically pure inherently chiral calixarenoacetic acid derivatives with asymmetric arrangement of substituents on the lower rim were synthesized. A detailed study of the enantiobinding properties of such compounds in relation to various of its nature chiral analytes was carried out. A fruitful approach for the synthesis of inherently chiral calix[4]arenes with an asymmetric arrangement of substituents on the upper rim was proposed and investigated, which consists in sequential regioselective substitution of the para-positions of phenolic fragments with a free OH group and selective hydrolysis of benzoyl groups in readily available 25,26-dibenzoyloxy-27-propyloxy-28-hydroxy-calix[4]arene.

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Research papers

Karpus, A.; Yesypenko, O.; Cherenok, S.; Boiko, V.; Kalchenko, O.; Voitenko, Z.; Tribrat, O.; Poli, R.; Daran, J.-C.; Manoury, E.; Kalchenko, V. Chiral phosphorus-containing calixarenes. Phosphorus, Sulfur and Silicon 2019, 194 (4-6), 471-475. DOI: 10.1080/10426507.2018.1539994

Yesypenko, O. A.; Osipova, A. O.; Tribrat, O. O.; Kravchenko, S. O.; Usachov, O. M.; Dyakonenko, V. V.; Ryabitskii, A. B.; Pirozhenko, V. V.; Shishkina, S. V.; Rozhenko, A. B.; Kalchenko, V. I. Synthesis and enantiorecognition properties of stereoisomeres of inherently chiral propyloxy-octyloxy-calix[4]arene acetic acids. Tetrahedron 2021, 80, article 131894. DOI: 10.1016/j.tet.2020.131894

Trybrat, O. O.; Yesypenko, O. A.; Shishkina, S. V.; Rusanov, E. B.; Karpichev, E. A.; Kalchenko, V. I. 25-Propyloxy-26,27-dibenzoyloxy-calix[4]arene as precursor of inherently chiral calixarenes with AB and ABC substitution patterns at the upper rim. European Journal of Organic Chemistry 2021, 28, 3912-3919. DOI: 10.1002/ejoc.202100624

Kalchenko, O. I.; Trybrat, O. O.; Yesypenko, O. A.; Dyakonenko, V. V.; Shishkina, S. V.; Kalchenko, V. I. Inherently chiral dialkyloxy-calix[4]arene acetic acids as enantiodiscriminating additives for high-performance liquid chromatography separation of D,L-amino acids. Chirality 2021, 33 (10), 722-730. DOI: 10.1002/chir.23355

Kazantseva, Z. I.; Koshets, I. A.; Trybrat, O. O.; Yesypenko, O. A.; Kalchenko, V. I. Recognition of 1-phenylethylamine enantiomers by thin solid films of inherently chiral calix[4]arene. Chirality 2021, 33 (10), 703-709. DOI: 10.1002/chir.23351

Yesypenko, O. A.; Trybrat, O. O.; Vashchenko O. O.; Suikov, S. Yu. Influence of the configuration of an asymmetric carbon center on the parameters of the nuclear magnetic resonance spectra of inherently chiral N-(1-phenylethyl)amides of calix[4]arene acetic acids: determination of the absolute stereochemical configuration of the macrocycle. Theoretical and Experimental Chemistry 2022, 58 (1), 54-60. DOI: 10.1007/s11237-022-09722-9

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