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Orbital Crossings Activated through Electron Injection: Opening Communication between Orthogonal Orbitals in Anionic C1–C5 Cyclizations of Enediynesстатья
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: 6 февраля 2017 г.
- Авторы: Peterson Paul W., Nikolay Shevchenko, Boris Breiner, Mariappan Manoharan, Forat Lufti, Jess Delaune, Margaret Kingsley, Kirill Kovnir, Igor Alabugin
- Журнал: Journal of the American Chemical Society
- Том: 138
- Номер: 48
- Год издания: 2016
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 15617
- Последняя страница: 15628
- DOI: 10.1021/jacs.6b08540
- Аннотация: Generally, the long-range electronic communication between spatially orthogonal orbitals is inefficient and limited to field and inductive effects. In this work, we provide experimental evidence that such communication can be achieved via intramolecular electron transfer between two degenerate and mutually orthogonal frontier molecular orbitals (MOs) at the transition state. Interaction between orthogonal orbitals is amplified when the energy gap between these orbitals approaches zero, or at an “orbital crossing”. The crossing between two empty or two fully occupied MOs, which do not lead to stabilization, can be “activated” when one of the empty MOs is populated (i.e., electron injection) or one of the filled MOs is depopulated (i.e., hole injection). In reductive cycloaromatization reactions, such crossings define transition states with energies defined by both the in-plane and out-of-plane π-systems. Herein, we provide experimental evidence for the utility of this concept using orbital crossings in reductive C1–C5 cycloaromatization reactions of enediynes. Communication with remote substituents via orbital crossings greatly enhances regioselectivity of the ring closure step in comparison to the analogous radical cyclizations. We also present photophysical data pertaining to the efficiency of electron injection into the benzannelated enediynes.
- Добавил в систему: Шевченко Николай Евгеньевич