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
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Otros documentos de la autoría: Adjieufack, Abel Idrice; Moto Ongagna , Jean; Essomba, Jean Serge; Ewonkem, Monique; Oliva, Mónica; Safont Villarreal, Vicent Sixte; Andres, Juan
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Título
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 TheoryAutoría
Fecha de publicación
2023Editor
MDPICita bibliográfica
Adjieufack, A.I.; Ongagna, J.M.; Essomba, J.S.; Ewonkem, M.B.; Oliva, M.; Safont, V.S.; Andrés, J. Exploring the Mechanism of the Intramolecular Diels–Alder Reaction of (2E,4Z,6Z)-2(allyloxy)cycloocta2,4,6-trien-1-one Using Bonding Evolution Theory. Molecules 2023, 28, 6755. https://doi.org/10.3390/ molecules28196755Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
https://www.mdpi.com/1420-3049/28/19/6755Versión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
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) ... [+]
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. [-]
Publicado en
Molecules, 2023Entidad financiadora
FNRS-FRFC | University of Namur | Generalitat Valenciana | Universitat Jaume I
Código del proyecto o subvención
No. 2.5020.11 | GEQ U.G006.15 | 1610468 | RW/GEQ2016 | CIAICO/2021/122 | UJI-B2022-56
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