Yakovenko A. Synthesis and properties of calix[4]arenes possessing aminocarbonyl and sulfonyl moieties

The Thesis is devoted to the synthesis of aminocarbonyl, guanidinium calixarenes and calixarenesulfonyl derivatives; development of the method and synthesis of inherently chiral calix[4]arenes; study of the chemical and anion-binding properties. A series of mono-, di- and tetracarbamates have been obtained by the reaction of acylisocyanates with hydroxycalix[4]arenes. Acylcarbamate moiety of mocarbamates is an effective protective group for the selective modification of calix[4]arene platform. A convenient method of synthesis of isocynatocalixarenes has been developed. By the nucleophilic addition of the esters of L-amino acids appropriate ureas have been obtained. By NMR-CIS technique it was found, that L-alanine derivatives bind in acetone D-phenylalaninate anion 4 times more strongly than L-form. Camphorsulfonylation of monoisopropoxycalix[4]arenes gives appropriate proximal derivatives obtained as a mixture of diastereomers with high yields. An absolute configuration of both diastereomers has beenestablished by means of an X-ray diffraction method. By simple bromination reaction and alkaline hydrolysis enantiomerically pure dibromomonoisopropoxy calixarene has been synthesized.