Diverse Cyclization Pathways Between Nitriles with Active α-Methylene Group and Ambiphilic 2-Pyridylselenyl Reagents Enabled by Reversible Covalent Bonding
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.
Authors
- Anton R. Egorov (ORCID: https://orcid.org/0000-0002-6006-6883)
- Alexander G. Tskhovrebov (ORCID: https://orcid.org/0000-0002-4445-2530)
- Ж. В. Мацулевич (ORCID: https://orcid.org/0000-0002-0858-5897)
- Namiq Q. Shikhaliyev (ORCID: https://orcid.org/0000-0002-6842-151X)
- Rosa M. Gomila (ORCID: https://orcid.org/0000-0002-0827-8504)
- Victor N. Khrustalev (ORCID: https://orcid.org/0000-0001-8806-2975)
- Alexander A. Sapronov (ORCID: https://orcid.org/0000-0003-2647-8865)
- А. В. Борисов (ORCID: https://orcid.org/0000-0003-1765-5241)
- Antonio Frontera (ORCID: https://orcid.org/0000-0001-7840-2139)
- Alexander S. Novikov (ORCID: https://orcid.org/0000-0001-9913-5324)
- Alexey A. Artemjev
- Аlexander S. Peregudov (ORCID: https://orcid.org/0000-0001-6223-0184)
- Valentine G. Nenajdenko (ORCID: https://orcid.org/0000-0001-9162-5169)
- Alexey S. Kubasov (ORCID: https://orcid.org/0000-0002-0156-5535)
- Andreii Sergeevich Kritchenkov (ORCID: https://orcid.org/0000-0002-6411-5988)
Institutions
- Peoples' Friendship University of Russia (RU)
- Lomonosov Moscow State University (RU)
- Kurchatov Institute (RU)
- A. N. Nesmeyanov Institute of Organoelement Compounds (RU)
- N.D. Zelinsky Institute of Organic Chemistry (RU)
- Institute of Macromolecular Compounds (RU)
- NS Kurnakova Institute of General and Inorganic Chemistry (RU)
- Petersburg Nuclear Physics Institute (RU)
- Nizhny Novgorod State Technical University (RU)
- Baku Engineering University (AZ)
- Nizhny Novgorod State Pedagogical University (RU)
- Universitat de les Illes Balears (ES)
Publication Details
- Journal
- International Journal of Molecular Sciences
- Published
- 2024-11-28
- DOI
- https://doi.org/10.3390/ijms252312798
- Citations
- 8
- Primary Topic
- Chemical Synthesis and Analysis
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- Russian Science Foundation
- Ministry of Science and Higher Education of the Russian Federation
- RUDN University
- Agencia Estatal de Investigación