|
ИСТИНА |
Войти в систему Регистрация |
ИПМех РАН |
||
Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetatesстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Vil V.A., Gorlov E.S., Shuingalieva D.V., Kunitsyn A.Y., Krivoshchapov N.V., Medvedev M.G., Alabugin I.V., Terent’Ev A.O.
- Журнал: Journal of Organic Chemistry
- Том: 87
- Номер: 21
- Год издания: 2022
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 13980
- Последняя страница: 13989
- DOI: 10.1021/acs.joc.2c01634
- Аннотация: The reactions of O-electrophiles, such as organic peroxides, with carbon nucleophiles are an umpolung alternative to the common approaches to C-O bond formation. Nucleophilic substitution at the oxygen atom of cyclic diacyl peroxides by enol acetates with the following deacylation leads to α-acyloxyketones with an appended carboxylic acid in 28-87% yields. The effect of fluorinated alcohols on the oxidative functionalization of enol acetates by cyclic diacyl peroxides was studied experimentally and computationally. Computational analysis reveals that the key step proceeds as a direct substitution nucleophilic bimolecular (SN2) reaction at oxygen (SN2@O). CF3CH2OH has a dual role in assisting in both steps of the reaction cascade: it lowers the energy of the SN2@O activation step by hydrogen bonding to a remote carbonyl and promotes the deacylation of the cationic intermediate. © 2022 American Chemical Society. All rights reserved.
- Добавил в систему: Малошицкая Ольга Александровна