Palladium-catalyzed C(sp3)-H activation in a monoterpene-based compound under mild conditions: a combined experimental and theoretical mechanistic study

Palladium-catalyzed C(sp3)-H activation in a monoterpene-based compound under mild conditions: a combined experimental and theoretical mechanistic study Full article

Journal

ChemPlusChem
ISSN: 1212-6950 , E-ISSN: 0010-0765

Output data

Year: 2025, Volume: 90, Number: 1, Article number : e202400509, Pages count : 8 DOI: 10.1002/cplu.202400509

Tags

sp3 C-H bond activation, complex, palladium, monoterpene

Authors

Kokina Tatiana E. ¹ , Shekhovtsov Nikita A. ¹ , Tkachev Alexey V. ² , Agafontsev Alexander M. ² , Gourlaouen Christophe ³ , Bushuev Mark B. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences 3, Acad. Lavrentiev Ave., Novosibirsk 630090, Russia
2	N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences 3, Acad. Lavrentiev Ave., Novosibirsk 630090, Russia
3	Laboratoire de Chimie Quantique Institut de Chimie, UMR 7177 CNRS-Université de Strasbourg 4 rue Blaise Pascal, 67070 Strasbourg Cedex, France

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.

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

Submitted:	Jul 29, 2024
Accepted:	Sep 13, 2024
Published print:	Nov 1, 2024
Published online:	Jan 15, 2025

Web of science:	WOS:001357160800001
Scopus:	2-s2.0-85207762155
Elibrary:	73736238
OpenAlex:	W4402512094

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