Palladium-catalyzed C(sp3)-H activation in a monoterpene-based compound under mild conditions: a combined experimental and theoretical mechanistic study Научная публикация
Журнал |
ChemPlusChem
ISSN: 1212-6950 , E-ISSN: 0010-0765 |
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Вых. Данные | Год: 2025, Том: 90, Номер: 1, Номер статьи : e202400509, Страниц : 8 DOI: 10.1002/cplu.202400509 | ||||||
Ключевые слова | sp3 C-H bond activation, complex, palladium, monoterpene | ||||||
Авторы |
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Организации |
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Реферат:
The first example of the palladium-catalyzed sp3 C-H bond activation in a monoterpene-based compound has been observed in the reaction of PdCl2 with a (+)-3-carene-based ligand HL (HL = N-((1aS,3S,7bR)-1,1,3-trimethyl-7-phenyl-5-(pyridin-2-yl)-1a,2,3,7b-tetrahydro-1H-cyclopropa[f]quinolin-3-yl)acetamide), which yielded the [PdLCl] complex. In contrast to the vast majority of C(sp3)-H activation reactions which require prolonged heating and mixing due to the inert character of the corresponding bond, the reaction reported herein proceeds rapidly under mild conditions. A theoretical insight into the ligand deprotonation has been performed by DFT calculations. The mechanism of the C-H activation involves (i) simultaneous coordination of the CH3 group of HL to the Pd2+ ion and decoordination of the Cl- anion with consequent formation of a Cl⋅⋅⋅H-N hydrogen bond with the amide group, (ii) approximation of the out-of-sphere Cl- anion to one of the hydrogen atoms of the CH3 group mediated by the crane motion of the amide group and (iii) the ejection of the HCl molecule, which increases the entropy of the system and serves as a driving force for the reaction.
Библиографическая ссылка:
Kokina T.E.
, Shekhovtsov N.A.
, Tkachev A.V.
, Agafontsev A.M.
, Gourlaouen C.
, Bushuev M.B.
Palladium-catalyzed C(sp3)-H activation in a monoterpene-based compound under mild conditions: a combined experimental and theoretical mechanistic study
ChemPlusChem. 2025. V.90. N1. e202400509 :1-8. DOI: 10.1002/cplu.202400509 WOS Scopus РИНЦ OpenAlex
Palladium-catalyzed C(sp3)-H activation in a monoterpene-based compound under mild conditions: a combined experimental and theoretical mechanistic study
ChemPlusChem. 2025. V.90. N1. e202400509 :1-8. DOI: 10.1002/cplu.202400509 WOS Scopus РИНЦ OpenAlex
Даты:
Поступила в редакцию: | 29 июл. 2024 г. |
Принята к публикации: | 13 сент. 2024 г. |
Опубликована в печати: | 1 нояб. 2024 г. |
Опубликована online: | 15 янв. 2025 г. |
Идентификаторы БД:
Web of science: | WOS:001357160800001 |
Scopus: | 2-s2.0-85207762155 |
РИНЦ: | 73736238 |
OpenAlex: | W4402512094 |
Цитирование в БД:
Пока нет цитирований