Effective self-assembly of 21- and 14-membered azamacrocycles via condition-controlled cyclotrimerization or cyclodimerization of different thiosemicarbazide-based precursors

A preparative synthesis of previously unknown 21- and 14-membered azamacrocycles acid-promoted cyclotrimerization or cyclodimerization of three readily available precursors, namely, 1-amino-6-hydroxy-4,6-dimethylhexahydropyrimidine-2-thione, 4-(4-oxopent-2-yl)thiosemicarbazide hydrazone, and 5,7-dim...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2024-11, Vol.22 (46), p.9078-9093
Main Authors: Fesenko, Anastasia A, Grigoriev, Mikhail S, Shutalev, Anatoly D
Format: Article
Language:English
Subjects:
Hydrazones
Precursors
Self-assembly
Thiosemicarbazides
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Summary:A preparative synthesis of previously unknown 21- and 14-membered azamacrocycles acid-promoted cyclotrimerization or cyclodimerization of three readily available precursors, namely, 1-amino-6-hydroxy-4,6-dimethylhexahydropyrimidine-2-thione, 4-(4-oxopent-2-yl)thiosemicarbazide hydrazone, and 5,7-dimethyl-1,4,5,6-tetrahydro-3 -1,2,4-triazepine-3-thione has been developed. A dramatic dependence of the selectivity of macrocyclization on the reaction conditions is demonstrated. The thermodynamic aspects of the reactions are discussed based on experimental data and DFT calculation results. Plausible pathways for the formation of macrocycles are proposed.
ISSN:1477-0520
1477-0539
1477-0539
DOI:10.1039/d4ob01384k