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Pd-Catalyzed Synthesis of Densely Functionalized Cyclopropyl Vinyl Sulfides Reveals the Origin of High Selectivity in a Fundamental Alkyne Insertion Stepстатья Исследовательская статья
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: 3 марта 2021 г.
- Авторы: Sahharova Liliya T., Gordeev Evgeniy G., Eremin Dmitry B., Ananikov Valentine P.
- Журнал: ACS catalysis
- Том: 10
- Номер: 17
- Год издания: 2020
- Издательство: American Chemical Society
- Местоположение издательства: United States
- Первая страница: 9872
- Последняя страница: 9888
- DOI: 10.1021/acscatal.0c02053
- Аннотация: Catalytic atom-economic hydrothiolation of cyclopropyl acetylenes was developed. Using Pd/NHC complex as a precatalyst, regioselective addition of thiols to cyclopropyl acetylenes was successfully performed, leading to densely functionalized compounds in excellent selectivity (up to 99:1) and high yields (up to 99%). Formation of Markovnikov-type products by insertion of alkyne into the Pd–S bond was confirmed experimentally. Molecular dynamics of the alkyne insertion into the Pd–S bond was performed computationally to identify key factors controlling the remarkable regioselectivity of this process. The fundamental question of how a small difference in activation energies can result in very high regioselectivity has been addressed by experimental methods combined with computational modeling. We show that the insertion of alkyne into the Pd–S bond proceeds by an asynchronous mechanism, which starts with metal–carbon binding and resolves into diverse transient structures. We further demonstrate that dynamic involvement of these structures ensures regioselectivity of the entire process, thus providing a mechanistic link that has long been missing. Alkyne insertion into the metal–heteroatom bond is a fundamental elementary step and a corner stone of catalysis and organometallic chemistry that works for a large variety of metals and heteroatoms. Mastering its Markovnikov vs anti-Markovnikov selectivity provides powerful opportunities for the design of selective functionalization routes.
- Добавил в систему: Анаников Валентин Павлович