Theoretical Study for the [2+2] Cycloaddition Reaction Mechanism of Ketenes and their Derivatives

Mohammad‐Salim, Haydar A.; Abdallah, Hassan H.

doi:10.13005/ojc/350512

Cited by 7 publications

(3 citation statements)

References 30 publications

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“…Eventually, the fourmembered ring compound relaxes back to the ground state and forms a four-membered ring copolymer (Co-adduct). 32,[36][37][38][39] To further figure out the reaction process of self-sensitized [2 + 2] photocycloaddition, the energy barrier of each reaction process was explored by DFT calculation, with the results shown in Figure 4.…”

Section: Optimization Of [2 + 2] Photocycloaddition Reaction Conditionsmentioning

confidence: 99%

Mechanism and kinetics of self‐sensitized photocycloaddition of cyclohexenone and norbornene

Chen,

Zhang,

Guo

et al. 2024

AIChE Journal

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Solar‐driven conversion of renewable biomass resources into high‐density hydrocarbon fuels can effectively realize biomass valorization and renewable energy conversion. In this work, an efficient self‐sensitized [2 + 2] photocycloaddition process is explored to develop highly strained fuel with high yield using norbornene and biomass‐derived cyclohexenone as feedstocks. The enhancement mechanism is revealed by phosphorescent measurement and theoretical calculation, and a reasonable reaction path for self‐sensitized [2 + 2] co‐cycloaddition is proposed. When using methanol as solvent, the apparent activation energy of co‐cycloaddition is 21.37 W/mol, which is lower than that of self‐cycloaddition (31.57 W/mol). Importantly, the jet‐fuel‐range highly strained fuel has high density (0.986 g/cm3) and high volumetric net heat of combustion (41.14 MJ/L), which are 5.34% and 4.39% higher than those of JP‐10, respectively. This work proposes a green and effective pathway for the preparation of high‐performance hydrocarbon fuel with polycyclic‐asymmetric structure.

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Section: Optimization Of [2 + 2] Photocycloaddition Reaction Conditionsmentioning

confidence: 99%

Mechanism and kinetics of self‐sensitized photocycloaddition of cyclohexenone and norbornene

Chen,

Zhang,

Guo

et al. 2024

AIChE Journal

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“…In the last two decades, computational chemistry has become an important instrument for analyzing experimentally reported reactivity and selectivity results by constructing a comprehensive picture of how chemical events occur [16][17][18][19][20][21][22][23][24]. In 2016, Domingo [25] proposed the Molecular Electron Density Theory (MEDT), recognizing the critical role of electron density changes in molecular reactivity.…”

Section: Introductionmentioning

confidence: 99%

Theoretical insight into the mechanism and selectivity of the [3 + 2] cycloaddition reaction of N-methyl-1-phenylmethanimine oxide and bicyclopropylidene from the MEDT perspective

Mohammad‐Salim¹,

Julián-Ortiz²

2023

Struct Chem

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The mechanism and regioselectivity of [3+2] cycloaddition (32CA) reactions of N-methyl-1phenylmethanimine oxide nitrone 1 and bicyclopropylidene 2 are analyzed using molecular electron density theory (MEDT) at the B3LYP/6-311++G(d,p) level. A study of the electron localisation function (ELF) predicts the zwitter-ionic nature of the nitrone, allowing its participation in zw-type 32CA reactions with a high energy barrier that must be surmounted by suitable electrophilic-nucleophilic interactions. The global electronic flux from the strong nucleophilic bicyclopropylidene 2 to the electrophilic nitrone 1 is predicted by an analysis of the CDFT indices. In this 32CA reaction, no new covalent bonds are generated at the TSs, and the mechanism is one-step and kinetically controlled with low asynchronous bond production.The Gibbs free energy of this 32CA reaction in the gas phase is -9.88 and -15.01 kcal.mol -1 for exo and endo path, respectively. The increased thermodynamic stability of the cycloadducts 4 favors the endo regiochemical route. The ELF topological examination at the transition stages is in agreement with the predictions of bonding evolution theory (BET) for the endo and exo routes, which point to a one-step process including early transition states.

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“…Computational studies on cycloaddition reactions, in recent years, have been the subject of a number of researches due to their wide applications on synthetic organic compounds [1][2][3][4][5]. Among cycloadditions, [3+2] cycloaddition reactions (32CAs) represent versatile process for the synthesis of a system with five membered ring and a large variety of heterocyclic compounds can be synthesized relying on the choice of the three-atom-component (TAC) and the alkenes derivative [6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Understanding the Reactivity of C-Cyclopropyl-N-Methylnitrone Participating in [3+2] Cycloaddition Reactions Towards Styrene with a Molecular Electron Density Theory Perspective

Mohammad‐Salim

2021

J. Mex. Chem. Soc.

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Abstract. The [3+2] cycloaddition (32CA) reactions of C-cyclopropyl-N-methylnitrone 1 with styrene 2 have been studied within molecular electron density theory (MEDT) at the B3LYP/6-311++G(d,p) level of theory. These zwitterionic type 32CA reactions occur through a one-step mechanism. The 32CA reactions undergo four stereo- and regioisomeric reaction paths to form four different products, 3, 4, 5 and 6. Analysis of the conceptual density functional theory (CDFT) indices predict the global electronic flux from the strong nucleophilic nitrone 1 to the styrene 2. These 32CA reactions are endergonic with reactions Gibbs free energies between 2.83 and 7.39 kcal.mol-1 in the gas phase. The 32CA reaction leading to the formation of cycloadduct 3 presents the lowest activation enthalpy than the other paths due to a slightly increase in polar character evident from the global electron density transfer (GEDT) at the transition states and along the reaction path. The bonding evolution theory (BET) study suggests that these 32CA reactions occur through the coupling of pseudoradical centers and the formation of new C-C and C-O covalent bonds has not been started in the transition states. Resumen.

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Theoretical Study for the [2+2] Cycloaddition Reaction Mechanism of Ketenes and their Derivatives

Cited by 7 publications

References 30 publications

Mechanism and kinetics of self‐sensitized photocycloaddition of cyclohexenone and norbornene

Mechanism and kinetics of self‐sensitized photocycloaddition of cyclohexenone and norbornene

Theoretical insight into the mechanism and selectivity of the [3 + 2] cycloaddition reaction of N-methyl-1-phenylmethanimine oxide and bicyclopropylidene from the MEDT perspective

Understanding the Reactivity of C-Cyclopropyl-N-Methylnitrone Participating in [3+2] Cycloaddition Reactions Towards Styrene with a Molecular Electron Density Theory Perspective

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