The first approach to highly substituted dihydroimidazotriazolones and their controlled post-transformations
4 affiliations
- 1Institute of Functional Materials Chemistry, State Scientific Institution “Institute for Single Crystals” of National Academy of Sciences of Ukraine, Nauky Avenue 60, Kharkiv, Ukraine, 61072
- 2Institute of Organic Chemistry National Academy of Sciences of Ukraine, Akademik Kukhar Street 5, Kyiv, 02660
- 3Education and Research Institute of Chemistry, V. N. Karazin Kharkiv National University, Svobody Square 4, Kharkiv, Ukraine, 61022
- 4Department of Organic Chemistry, Biochemistry, Paints and Coatings, National Technical University “Kharkiv Polytechnic Institute”, Kyrpychova Street 2, Kharkiv, Ukraine, 61002
Abstract
A novel class of azido-modified α , β -unsaturated Ugi adducts (enamides) has been explored as a versatile platform for post -Ugi transformations. While intramolecular azide-alkyne cycloadditions of Ugi-derived peptidomimetics have been extensively studied, the corresponding azide-alkene cycloadditions on similar scaffolds have remained unexplored. In this work, we report a systematic investigation of intramolecular azide-alkene cycloaddition involving activated enamide moieties derived from Ugi adducts. Enamides readily undergo catalyst-free intramolecular [3+2] cycloaddition under mild conditions to afford the previously unknown 3,3a,4-trisubstituted-3a,4-dihydro-3 H -imidazo[1,2-c][1,2,3]triazol-5(6 H )-one scaffold in high yields. This novel fused heterocyclic system was fully characterised and proved to be a highly versatile intermediate for divergent post -Ugi transformations. Fused dihydrotriazoles transformed into 3,5-dihydroimidazol-4-ones via an elimination of N 2 supplemented by acylamide migration. Additionally, base- or acid-mediated cascades enabled efficient one-pot access to aromatised 1,2,3-triazoles and open-chain triamides, respectively. In total, 4 generations of structural isomers and 2 other classes of compounds were involved in the work. The methodologies developed highlight the synthetic value of azido-modified enamides as divergent intermediates, providing rapid and controlled entry to structurally diverse nitrogen-rich heterocycles and peptidomimetics from simple Ugi adducts derived from α , β- unsaturated aldehydes.
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BibTeX
@misc{vereshchak2026first,
title = {{The first approach to highly substituted dihydroimidazotriazolones and their controlled post-transformations}},
author = {Vladyslav Vereshchak and Viacheslav Saraiev and Vladimir Musatov and Svitlana Shishkina and Valentyn Chebanov and Alexander Tsygankov},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009125/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009125/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - The first approach to highly substituted dihydroimidazotriazolones and their controlled post-transformations
AU - Vladyslav Vereshchak
AU - Viacheslav Saraiev
AU - Vladimir Musatov
AU - Svitlana Shishkina
AU - Valentyn Chebanov
AU - Alexander Tsygankov
PY - 2026
DA - 2026/09/21
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009125/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009125/v1
AB - A novel class of azido-modified α , β -unsaturated Ugi adducts (enamides) has been explored as a versatile platform for post -Ugi transformations. While intramolecular azide-alkyne cycloadditions of Ugi-derived peptidomimetics have been extensively studied, the corresponding azide-alkene cycloadditions on similar scaffolds have remained unexplored. In this work, we report a systematic investigation of intramolecular azide-alkene cycloaddition involving activated enamide moieties derived from Ugi adducts. Enamides readily undergo catalyst-free intramolecular [3+2] cycloaddition under mild conditions to afford the previously unknown 3,3a,4-trisubstituted-3a,4-dihydro-3 H -imidazo[1,2-c][1,2,3]triazol-5(6 H )-one scaffold in high yields. This novel fused heterocyclic system was fully characterised and proved to be a highly versatile intermediate for divergent post -Ugi transformations. Fused dihydrotriazoles transformed into 3,5-dihydroimidazol-4-ones via an elimination of N 2 supplemented by acylamide migration. Additionally, base- or acid-mediated cascades enabled efficient one-pot access to aromatised 1,2,3-triazoles and open-chain triamides, respectively. In total, 4 generations of structural isomers and 2 other classes of compounds were involved in the work. The methodologies developed highlight the synthetic value of azido-modified enamides as divergent intermediates, providing rapid and controlled entry to structurally diverse nitrogen-rich heterocycles and peptidomimetics from simple Ugi adducts derived from α , β- unsaturated aldehydes.
ER -