Résumé
In the present work, the bond breaking/forming events along the intramolecular Diels–Alder (IMDA) reaction of (2E,4Z,6Z)-2(allyloxy)cycloocta-2,4,6-trien-1-one have been revealed within bonding evolution theory (BET) at the density functional theory level, using the M05-2X functional with the cc-pVTZ basis set. Prior to achieving this task, the energy profiles and stationary points at the potential energy surface (PES) have been characterized. The analysis of the results finds that this rearrangement can proceed along three alternative reaction pathways (a–c). Paths a and b involve two steps, while path c is a one-step process. The first step in path b is kinetically favored, and leads to the formation of an intermediate step, Int-b. Further evolution from Int-b leads mainly to 3-b1. However, 2 is the thermodynamically preferred product and is obtained at high temperatures, in agreement with the experimental observations. Regarding the BET analysis along path b, the breaking/forming process is described by four structural stability domains (SSDs) during the first step, which can be summarized as follows: (1) the breaking of the C–O bond with the transfer of its population to the lone pair (V(O)), (2) the reorganization of the electron density with the creation of two V(C) basins, and (3) the formation of a new C–C single bond via the merger of the two previous V(C) basins. Finally, the conversion of Int-b (via TS2-b1) occurs via the reorganization of the electron density during the first stage (the creation of different pseudoradical centers on the carbon atoms as a result of the depopulation of the C–C double bond involved in the formation of new single bonds), while the last stage corresponds to the non-concerted formation of the two new C–C bonds via the disappearance of the population of the four pseudoradical centers formed in the previous stage. On the other hand, along path a, the first step displays three SSDs, associated with the depopulation of the V(C2,C3) and V(C6,C7) basins, the appearance of the new monosynaptic basins V(C2) and V(C7), and finally the merging of these new monosynaptic basins through the creation of the C2–C7 single bond. The second step is described by a series of five SSDs, that account for the reorganization of the electron density within Int-a via the creation of four pseudoradical centers on the C12, C13, C3 and C6 carbon atoms. The last two SSDs deal with the formation of two C-C bonds via the merging of the monosynaptic basins formed in the previous domains.
langue originale | Anglais |
---|---|
Numéro d'article | 6755 |
journal | Molecules |
Volume | 28 |
Numéro de publication | 19 |
Les DOIs | |
Etat de la publication | Publié - oct. 2023 |
Financement
A.I.A. thanks the University of Namur (Belgium) for his UNamur-CERUNA Ph.D. Mobility Fellowship. The calculations were performed on the computers at the Consortium des Equipements de Calcul Intensif (CECI, http://www.ceci-hpc.be , accessed on 15 April 2023) and particularly those of the Technological Platform of High-Performance Computing, for which the authors gratefully acknowledge the financial support of the FNRS-FRFC, in the Walloon Region, and of the University of Namur (Conventions No. 2.5020.11, GEQ U.G006.15, 1610468, and RW/GEQ2016). JA, MO and VSS are grateful for the financial support from the Generalitat Valenciana (Grant CIAICO/2021/122) and Universitat Jaume I (Grant UJI-B2022-56). This research was funded by FNRS-FRFC, in the Walloon Region, and the University of Namur, Conventions No. 2.5020.11, GEQ U.G006.15, 1610468, and RW/GEQ2016, as well as by Generalitat Valenciana, Grant CIAICO/2021/122, and Universitat Jaume I, Grant UJI-B2022-56.
Bailleurs de fonds | Numéro du bailleur de fonds |
---|---|
FNRS‐FRFC | |
Generalitat Valenciana | CIAICO/2021/122 |
Generalitat Valenciana | |
Universitat Jaume I | UJI-B2022-56 |
Universitat Jaume I | |
Université de Namur | 1610468, 2.5020.11, RW/GEQ2016, GEQ U.G006.15 |
Université de Namur |
Empreinte digitale
Examiner les sujets de recherche de « Exploring the Mechanism of the Intramolecular Diels–Alder Reaction of (2E,4Z,6Z)-2(allyloxy)cycloocta-2,4,6-trien-1-one Using Bonding Evolution Theory ». Ensemble, ils forment une empreinte digitale unique.Équipement
-
Plateforme Technologique Calcul Intensif
Champagne, B. (!!Manager)
Plateforme technologique Calcul intensifEquipement/installations: Plateforme technolgique