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Updated: Jun 9, 2025

Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
Effective self-assembly of 21- and 14-membered azamacrocycles via condition-controlled cyclotrimerization or
Anastasia A Fesenko1, Mikhail S Grigoriev1, Anatoly D Shutalev2
1A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Ave., 119071 Moscow, Russian Federation.
Abstract:
A preparative synthesis of previously unknown 21- and 14-membered azamacrocycles via 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-3H-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.
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