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Article

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

by
Alexey A. Artemjev
1,
Alexander A. Sapronov
1,
Alexey S. Kubasov
2,
Alexander S. Peregudov
3,
Alexander S. Novikov
1,
Anton R. Egorov
1,
Victor N. Khrustalev
1,4,
Alexander V. Borisov
5,
Zhanna V. Matsulevich
5,
Namiq G. Shikhaliyev
6,
Valentine G. Nenajdenko
7,
Rosa M. Gomila
8,
Antonio Frontera
8,
Andreii S. Kritchenkov
1,9 and
Alexander G. Tskhovrebov
1,*
1
Research Institute of Chemistry, Peoples’ Friendship University of Russia, 6 Miklukho-Maklaya Street, 117198 Moscow, Russia
2
Kurnakov Institute of General and Inorganic Chemistry, 31 Leninsky Prospekt, 119991 Moscow, Russia
3
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119334 Moscow, Russia
4
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, 119334 Moscow, Russia
5
Department of Chemistry, R.E. Alekseev Nizhny Novgorod State Technical University, Minin Street, 24, 603155 Nizhny Novgorod, Russia
6
Department of Chemical Engineering, Baku Engineering University, Hasan Aliyev Street 120, Baku AZ0101, Azerbaijan
7
Department of Chemistry, M.V. Lomonosov Moscow State University, 1 Leninskie Gory, 119991 Moscow, Russia
8
Departament de Química, Universitat de les Illes Balears, 07122 Palma de Mallorca, Spain
9
Branch of Petersburg Nuclear Physics Institute Named by B.P. Konstantinov of National Research Centre «Kurchatov Institute», Institute of Macromolecular Compounds, Bolshoi pr. VO 31, 199004 St. Petersburg, Russia
*
Author to whom correspondence should be addressed.
Int. J. Mol. Sci. 2024, 25(23), 12798; https://doi.org/10.3390/ijms252312798
Submission received: 5 November 2024 / Revised: 23 November 2024 / Accepted: 26 November 2024 / Published: 28 November 2024
(This article belongs to the Special Issue Noncovalent Interactions and Applications in Materials and Catalysis)
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Abstract

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.
Keywords: selenazoles; nitriles; non-covalent interactions; halogen bonding; chalcogen bonding selenazoles; nitriles; non-covalent interactions; halogen bonding; chalcogen bonding

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MDPI and ACS Style

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.; et al. Diverse Cyclization Pathways Between Nitriles with Active α-Methylene Group and Ambiphilic 2-Pyridylselenyl Reagents Enabled by Reversible Covalent Bonding. Int. J. Mol. Sci. 2024, 25, 12798. https://doi.org/10.3390/ijms252312798

AMA Style

Artemjev AA, Sapronov AA, Kubasov AS, Peregudov AS, Novikov AS, Egorov AR, Khrustalev VN, Borisov AV, Matsulevich ZV, Shikhaliyev NG, et al. Diverse Cyclization Pathways Between Nitriles with Active α-Methylene Group and Ambiphilic 2-Pyridylselenyl Reagents Enabled by Reversible Covalent Bonding. International Journal of Molecular Sciences. 2024; 25(23):12798. https://doi.org/10.3390/ijms252312798

Chicago/Turabian Style

Artemjev, Alexey A., Alexander A. Sapronov, Alexey S. Kubasov, Alexander S. Peregudov, Alexander S. Novikov, Anton R. Egorov, Victor N. Khrustalev, Alexander V. Borisov, Zhanna V. Matsulevich, Namiq G. Shikhaliyev, and et al. 2024. "Diverse Cyclization Pathways Between Nitriles with Active α-Methylene Group and Ambiphilic 2-Pyridylselenyl Reagents Enabled by Reversible Covalent Bonding" International Journal of Molecular Sciences 25, no. 23: 12798. https://doi.org/10.3390/ijms252312798

APA Style

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. (2024). Diverse Cyclization Pathways Between Nitriles with Active α-Methylene Group and Ambiphilic 2-Pyridylselenyl Reagents Enabled by Reversible Covalent Bonding. International Journal of Molecular Sciences, 25(23), 12798. https://doi.org/10.3390/ijms252312798

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