The mechanism of ionic Diels–Alder reactions. A DFT study of the oxa-Povarov reaction

Domingo, Luís R.; Aurell, M. J.; Pérez, Patricia

doi:10.1039/c3ra47805j

Cited by 27 publications

(25 citation statements)

References 54 publications

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“…2, 7, 9-10, 12, 28 14,16,18,24,27,55,58,71,76 It is expected that catalytic effects will be concerned almost exclusively with those factors that affects the charge polarization due to the departure of the chlorine atom from the C α center and the attaining of the planar configuration of the reaction center. The ELF topological analysis allows clearly establishing that reaction can be considered to take place through a two-stage one-step polar mechanism via a slightly asynchronous polar and quasi-planar transition structure.…”

Section: Discussionmentioning

confidence: 99%

Understanding the thermal dehydrochlorination reaction of 1-chlorohexane. Revealing the driving bonding pattern at the planar catalytic reaction center

et al. 2015

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The nature of bonding along the gas-phase thermal decomposition of 1-chlorohexane to produce 1-hexene and hydrogen chloride has been examined at the DFT M05-2X/6-311+G(d,p) level of theory. Based on results both from energetical and topological analysis of the electron localization function (ELF), we propose to rationalize the experimental available results not in terms of a decomposition via a four-membered cyclic transition structure (TS), but properly as a two stage one step reaction mechanism featuring a slightly asynchronous process associated to the catalytic planar reaction center at the TS. In this context, the first electronic stage corresponds to the ‫ܥ‬ ఋା ••• ‫݈ܥ‬ ఋି bond cleavage, which take place on the activation path earlier the transition structure be reached. There is no evidence of a Cl-C bond at the TS configuration. The second stage, associated to the top of the energy barrier, includes the TS and extends beyond on the deactivation pathway towards the products. The existence of both bonding and nonbonding non covalent interactions (NCI) are also revealed for the first time for the TS configuration. 17 47 to point -9 along the IRC reaction pathway. Arbitrarily the second stage concerning main electronic changes will be associated to points -9 to +9. Both stages refer to regions where key electronic changes driving the transformation take place. Note that from point -34 to point -5, the population associated to the disynaptic basin V(C α ,C β ) increases from 1.99e to 2.20e, whereas the population integrated in the disynaptic protonated basin V(H β ,C β ) decreases from 1.98e to 1.72e. The attractor corresponding to the forming double bond localizes out of the line connecting the carbon center cores. This topology for the C  -C  region remains unchanged until point 12 in region g. At the top of the energy barrier, within the entire interval IRC=(-0.97962,+0.97971), i.e., point -9 to point 9, we observe an isolated electron localization region integrating to 7.64e which is associated to the migrating chlorine center. This picture, on the top of the barrier, corresponds to a lonely chlorine atom bearing an electronic charge of -0.64 while evolving to the encounter of the H β center.Thereafter, within the tiny region d four valence monosynaptic basins V(Cl) associated to the negatively charged chlorine center adopt a tetrahedral conformation, with an increasing in the population from 7.64e to 7.70e. In this region the valence basins populations for V(C α ,C β ) and V(H β ,C β ) varies from 2.41e to 2.34e, and from 1.81e to 1.51e, respectively. The migrating chlorine center develops thus a maximum charge of -0.71 at the transition structure (point 0). ELF picture of bonding reveals that activation events are mainly associated to conformational changes in preparation of the reaction center (region a), followed by the breaking of the Cl-C α bond (regions b and c), and the start of the migration of H  atom with the associated bonding changes at C α -C β -H β moiety (regions c and d). Regarding t...

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Section: Discussionmentioning

confidence: 99%

Understanding the thermal dehydrochlorination reaction of 1-chlorohexane. Revealing the driving bonding pattern at the planar catalytic reaction center

et al. 2015

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“…Density functional theory (DFT) has been used widely and found as a very convenient method for getting reliable results and it has low computational cost (Cossío, et al, 1999;Liu, et al, 1998;Silva and Goodman, 2002). This method has been successfully used in many [4+2] cycloaddition reactions Domingo, et al, 2014;Fernández and Bickelhaupt, 2014;Ho, et al, 2016;Levandowski, et al, 2018;Rivero, et al, 2017b). Among these studies, computational works were compared with experimental to obtain detailed reaction mechanism, stero-and regioselectivity.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the [4+2] Cycloaddition Reaction of Trifluoroethylene with Five-membered Chalcogens Heterocyclic Compounds

Mohammad‐Salim

Abdallah

2019

ARO

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4+2] cycloaddition reaction has enormous significant in organic chemistry synthesis reactions and yet remains unexplored for the synthesis of fluorine-containing compounds. A density functional theory study of the stereo-and regioselectivity of the [4+2] cycloaddition reaction of trifluoroethylene with furan, thiophene, and selenophene was carried out in the gas phase. The B3LYP functional is used throughout in combination with 6-31G(d) basis set. The analysis of stationary points and the energetic parameters indicates that the reaction mechanism is concerted and confirms that the exo-adducts are thermodynamically and kinetically more favored than endo-adducts. The calculated branching ratio indicates that the exo-adducts have the higher percent yield than endoadducts and the yield of endo-adducts is increased only slightly on proceeding from furan, through thiophene, and onto selenophene. The analysis of the frontier molecular highest occupied molecular orbital (MO) and lowest unoccupied MO orbitals indicates that the exo-adducts are more stable due to their higher energy gab. The reaction energies were compared to the MP2/6-31G(d) and CCSD(T)/6-31G(d) calculations.Index Terms-Density functional theory, B3LYP, Regioselectivity, Stereoselectivity, [4+2] Cycloaddition.

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“…On the other hand, 1‐arylsulfonyl 1,3‐dienes possess the conjugated π system, which is bound with the ArSO 2 group. Thus, their reactivity towards the Diels–Alder or polar addition is of special current interest . In order to study the influence of the latter group, we have performed a series of S N reactions of 13 various 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes with such nucleophiles as diethylamine, diethanolamine, morpholine, potassium hydroxide, and sodium sulfide as well as the dehydrochlorination reaction yielding the corresponding 1‐arylsulfonyl 1,3‐dienes followed by the Diels–Alder addition with maleic anhydride.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, their reactivity towards the Diels-Alder or polar addition is of special current interest. [24][25][26][27][28][29] In order to study the influence of the latter group, we have performed a series of S N reactions of 13 various 1-(arylsulfonyl)-2-R-4-chloro-2-butenes with such nucleophiles as diethylamine, diethanolamine, morpholine, potassium hydroxide, and sodium sulfide as well as the dehydrochlorination reaction yielding the corresponding 1-arylsulfonyl 1,3-dienes followed by the Diels-Alder addition with maleic anhydride. Although 1-arylsulfonyl 1,3-dienes are expected to match better in the inverse electron demand Diels-Alder reaction, we have selected maleic anhydride as a dienophile because the latter yields crystalline adducts, which are used for the diene identification by characteristic melting points.…”

Section: Introductionmentioning

confidence: 99%

A combined experimental and density functional study of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes reactivity towards the allylic chlorine

Bondarchuk

Smalius

Minaev

2015

J. Phys. Org. Chem.

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Nucleophilic substitution and dehydrochlorination reactions of a number of the ring-substituted 1-(arylsulfonyl)-2-R-4-chloro-2-butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized by a general rapidity, cheapness, and simplicity providing moderate to high yields of 1-arylsulfonyl 1,3-butadienes (48-95%), 1-(arylsulfonyl)-2-R-4-(N,N-dialkylamino)-2-butenes (31-53%), 1-(arylsulfonyl)-2-R-2-buten-4-ols (37-61%), and bis[4-(arylsulfonyl)-3-R-but-2-enyl]sulfides (40-70%). The density functional theory B3LYP/6-311++G(2d,2p) calculations of the intermediate allylic cations in acetone revealed their high stability occurring from a resonance stabilization and hyperconjugation by the SO 2 Ar group. The reactivity parameters estimated at the bond critical points of the diene/allylic moiety display a high correlation (R 2 > 0.97) with the Hammett (σ p ) constants. 1-Arylsulfonyl 1,3-butadienes are characterized by a partly broken π conjugated system, which follows from analysis of the two-centered delocalization (δ) and localization (λ) index values. The highest occupied molecular orbital energies of 1-arylsulfonyl 1,3-butadienes are lower than those of 1,3-butadiene explaining their low reactivity towards the Diels-Alder condensation.

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The mechanism of ionic Diels–Alder reactions. A DFT study of the oxa-Povarov reaction

Abstract: Topological ELF analysis along these I-DA reactions indicates that both mechanisms present a similar C–C bond formation.

Cited by 27 publications

References 54 publications

Understanding the thermal dehydrochlorination reaction of 1-chlorohexane. Revealing the driving bonding pattern at the planar catalytic reaction center

Understanding the thermal dehydrochlorination reaction of 1-chlorohexane. Revealing the driving bonding pattern at the planar catalytic reaction center

Theoretical Study of the [4+2] Cycloaddition Reaction of Trifluoroethylene with Five-membered Chalcogens Heterocyclic Compounds

A combined experimental and density functional study of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes reactivity towards the allylic chlorine

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