Diverse Cyclization Pathways Between Nitriles with Active α-Methylene Group and Ambiphilic 2-Pyridylselenyl Reagents Enabled by Reversible Covalent Bonding

Artemjev, A.A.; Sapronov, A.A.; Kubasov, A.S.; Peregudov, A.S.; Novikov, A.S.; Egorov, A.R.; Khrustalev, V.N.; Borisov, A.V.; Matsulevich, Z.V.; Shikhaliyev, N.G.; Nenajdenko, V.G.; Gomila, R.M.; Frontera, A.; Kritchenkov, A.S.; Tskhovrebov, A.G.

Авторы: Artemjev Alexey A., Sapronov Alexander A., Kubasov Alexey S., Peregudov Alexander S., Novikov Alexander S., Egorov Anton R., Khrustalev Victor N., Borisov Alexander V., Matsulevich Zhanna V., Shikhaliyev Namiq G., Nenajdenko Valentine G., Gomila Rosa M., Frontera Antonio, Kritchenkov Andreii S., Tskhovrebov Alexander G.
Журнал: International Journal of Molecular Sciences
Том: 25
Номер: 23
Год издания: 2024
Издательство: MDPI
Местоположение издательства: Basel, Switzerland
Первая страница: 12798
Последняя страница: 12798
DOI: 10.3390/ijms252312798
Аннотация: Herein, we describe a novel coupling between ambiphilic 2-pyridylselenyl reagents and nitriles featuring an active α-methylene group. Depending on the solvent employed, this reaction can yield two distinct types of cationic pyridinium-fused selenium-containing heterocycles, 1,3-selenazolium or 1,2,4-selenadiazolium salts, in high yields. This is in contrast to what we observed before for other nitriles. Notably, the formation of selenadiazolium is reversible, gradually converting into the more thermodynamically stable selenazolium product in solution. Our findings reveal, for the first time, the reversible nature of 1,3-dipolar cyclization between the CN triple bond and 2-pyridylselenyl reagents. Nitrile substitution experiments in the adducts confirmed the dynamic nature of this cyclization, indicating potential applications in dynamic covalent chemistry. DFT calculations revealed the mechanistic pathways for new cyclizations, suggesting a concerted [3 + 2] cycloaddition for the formation of selenadiazolium rings and a stepwise mechanism involving a ketenimine intermediate for the formation of selenazolium rings. Natural bond orbital analysis confirmed the involvement of σ-hole interactions and lone pair to σ* electron donation in these processes. Additionally, theoretical investigations of σ-hole interactions were performed, focusing on the selenium-centered contacts within the new compounds.
Добавил в систему: Ненайденко Валентин Георгиевич

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Diverse Cyclization Pathways Between Nitriles with Active α-Methylene Group and Ambiphilic 2-Pyridylselenyl Reagents Enabled by Reversible Covalent Bondingстатья

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