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Peroxycarbenium Ions as the “Gatekeepers” in Reaction Design: Assistance from Inverse Alpha-Effect in Three-Component b-Alkoxy-b-peroxylactones Synthesisстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 24 января 2020 г.
- Авторы: Vil' Vera A., Barsegyan Yana A., Barsukov Denis V., Korlyukov Alexander A., Alabugin Igor V., Terent'ev Alexander O.
- Журнал: Chemistry - A European Journal
- Том: 25
- Номер: 63
- Год издания: 2019
- Издательство: John Wiley & Sons Ltd.
- Местоположение издательства: United Kingdom
- Первая страница: 14460
- Последняя страница: 14468
- DOI: 10.1002/chem.201903752
- Аннотация: Stereoelectronic interactions control reactivity of peroxycarbenium cations, the key intermediates in (per)oxidation chemistry. Computational analysis suggests that alcohol involvement as a third component in the carbonyl/peroxide reactions remained invisible due to the absence of sufficiently deep kinetic traps needed to prevent the escape of mixed alcohol/peroxide products to the more stable bisperoxides. Synthesis of β‐alkoxy‐β‐peroxylactones, a new type of organic peroxides, was accomplished by interrupting a thermodynamically driven peroxidation cascade. The higher energy β‐alkoxy‐β‐peroxylactones do not transform into the more stable bisperoxides due to the stereoelectronically imposed instability of a cyclic peroxycarbenium intermediate as a consequence of amplified inverse alpha‐effect. The practical consequence of this fundamental finding is the first three‐component cyclization/condensation of β‐ketoesters, H2O2, and alcohols that provides β‐alkoxy‐β‐peroxylactones in 15–80 % yields.
- Добавил в систему: Барсегян Яна Артуровна