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Inverse α-Effect as the Ariadne’s Thread on the Way to Tricyclic Aminoperoxides: Avoiding Thermodynamic Traps in the Labyrinth of Possibilitiesстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Yaremenko I.A., Belyakova Y.Y., Radulov P.S., Novikov R.A., Medvedev M.G., Krivoshchapov N.V., Korlyukov A.A., Alabugin I.V., Terent′ev A.O.
- Журнал: Journal of the American Chemical Society
- Том: 144
- Номер: 16
- Год издания: 2022
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 7264
- Последняя страница: 7282
- DOI: 10.1021/jacs.2c00406
- Аннотация: Stable tricyclic aminoperoxides can be selectively assembled via a catalyst-free three-component condensation of β,δ′-triketones, H2O2, and an NH-group source such as aqueous ammonia or ammonium salts. This procedure is scalable and can produce gram quantities of tricyclic heterocycles, containing peroxide, nitrogen, and oxygen cycles in one molecule. Amazingly, such complex tricyclic molecules are selectively formed despite the multitude of alternative reaction routes, via equilibration of peroxide, hemiaminal, monoperoxyacetal, and peroxyhemiaminal functionalities! The reaction is initiated by the "stereoelectronic frustration" of H2O2and combines elements of thermodynamic and kinetic control with a variety of mono-, bi-, and tricyclic structures evolving under the conditions of thermodynamic control until they reach a kinetic wall created by the inverse α-effect, that is, the stereoelectronic penalty for the formation of peroxycarbenium ions and related transition states. Under these conditions, the reaction stops before reaching the most thermodynamically stable products at a stage where three different heterocycles are assembled and fused at the acyclic precursor frame. © 2022 American Chemical Society. All rights reserved.
- Добавил в систему: Малошицкая Ольга Александровна