Secondary α-deuterium kinetic isotope effects in [2+4] cycloaddition of (E)-2-phenylnitroethene to cyclopentadiene

Kwiatkowska, Maria; Jasiński, Radomir; Mikulska, Maria; Barański, A.

doi:10.1007/s00706-010-0292-6

Cited by 13 publications

(10 citation statements)

References 20 publications

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“…In particular, the B3LYP/6-31G(d) calculations illustrate well the structure of transition states (TS) in cycloadditions between cyclopentadiene and CNA. This has been confirmed previously by the compilation of deuterium secondary kinetic isotope effects (SKIE) and results of quantum chemical calculations for polar Diels-Alder (P-DA [23] ) reaction between cyclopentadiene and (E)-2-phenylnitroethene [24]. The critical structures on the reaction paths were localized as in the case of the previously analysed reaction of (E)-2-phenyl-1-cyano-1-nitroethene with cyclopentadiene [22].…”

Section: Theoretical Exploration Of Reaction Pathssupporting

confidence: 78%

An experimental and theoretical study of the hetero Diels–Alder reactions between (E)-2-aryl-1-cyano-1-nitroethenes and ethyl vinyl ether: one-step or zwitterionic, two-step mechanism?

Jasiński

Kubik

Łapczuk-Krygier

et al. 2014

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The mechanistic aspects of the hetero Diels-Alder reactions between strongly electrophilic (E)-2-aryl-1-cyano-1-nitroethenes and ethyl vinyl ether have been analyzed on the basis of kinetic experimental results as well as quantum chemical simulations of reaction paths. These reactions may theoretically proceed via one step or stepwise, zwitterionic mechanism. It was found that the conversion of addends into adducts carried out via polar, but not zwitterionic mechanism. This is confirmed by kinetic substituent and solvent effects. Subsequently, a detailed analysis of internal reaction coordinate trajectories shows that the title reactions should be considered as examples of ''two-stage one-step'' cycloadditions according to Domingo terminology.

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Section: Theoretical Exploration Of Reaction Pathssupporting

confidence: 78%

An experimental and theoretical study of the hetero Diels–Alder reactions between (E)-2-aryl-1-cyano-1-nitroethenes and ethyl vinyl ether: one-step or zwitterionic, two-step mechanism?

Jasiński

Kubik

Łapczuk-Krygier

et al. 2014

Reac Kinet Mech Cat

Self Cite

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“…Presently it is known that the B3LYP calculations can illustrate the structure of the TSs in polar DA reactions involving cyclopentadiene, and this is confirmed by the compilation of deuterium secondary kinetic isotope effects and results of quantum chemical calculations for cycloaddition between cyclopentadiene and E-2-phenylnitroethene [131,132]. Additionally, in this study these results were also tested using the M06-2X/6-311 + G(d,p) method [133].…”

Section: Computational Detailssupporting

confidence: 66%

“…B3LYP/6-31G(d) Kohn-Sham wave functions have provided good predictions of potential surface energy (PES) that have been consistent with many experimental results [127][128][129][130][131]. Presently it is known that the B3LYP calculations can illustrate the structure of the TSs in polar DA reactions involving cyclopentadiene, and this is confirmed by the compilation of deuterium secondary kinetic isotope effects and results of quantum chemical calculations for cycloaddition between cyclopentadiene and E-2-phenylnitroethene [131,132].…”

Section: Computational Detailssupporting

confidence: 57%

Understanding the Polar Character Trend in a Series of Diels-Alder Reactions Using Molecular Quantum Similarity and Chemical Reactivity Descriptors

Morales-Bayuelo

Vivas‐Reyes

2014

Journal of Quantum Chemistry

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In molecular similarity there is a premise "similar molecules tend to behave similarly"; however in the actual quantum similarity field there is no clear methodology to describe the similarity in chemical reactivity, and with this end an analysis of charge-transfer (CT) processes in a series of Diels-Alder (DA) reactions between cyclopentadiene (Cp) and cyano substitutions on ethylene has been studied. The CT analysis is performed in the reagent assuming a grand canonical ensemble and the considerations for an electrophilic system using B3LYP/6-31 ( ) and M06-2X/6-311 + ( , ) methods. An analysis for CT was performed in agreement with the experimental results with a good statistical correlation ( 2 = 0.9118) relating the polar character to the bond force constants in DA reactions. The quantum distortion analysis on the transition states (TS) was performed using molecular quantum similarity indexes of overlap and coulomb showing good correlation ( 2 = 0.8330) between the rate constants and quantum similarity indexes. In this sense, an electronic reorganization based on molecular polarization in terms of CT is proposed; therefore, new interpretations on the electronic systematization of the DA reactions are presented, taking into account that today such electronic systematization is an open problem in organic physical chemistry. Additionally, one way to quantify the similarity in chemical reactivity was shown, taking into account the dependence of the molecular alignment on properties when their position changes; in this sense a possible way to quantify the similarity of the CT in systematic form on these DA cycloadditions was shown.

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“…It turned out that the TS-A transition state is a two-plane structure (Fig. 2), typical for one-step DA reactions between cyclopentadiene and ethylene derivatives [36][37][38][39]. Both new r-bonds are formed simultaneously within this structure.…”

Section: Key Structuresmentioning

confidence: 99%

A reexamination of the molecular mechanism of the Diels–Alder reaction between tetrafluoroethene and cyclopentadiene

Jasiński

2016

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DFT calculation results shed a new light on the mechanism of cycloaddition reaction between tetrafluoroethene and cyclopentadiene. The unique influence of fluorine atoms on the ethylene derivative molecule causes the [2 ? 2] cycloaddition process to take place according to a stepwise, biradical mechanism. At the same time, the competitive and independent path leads to a one-step (and not a twostep, as was once thought) cycloaddition reaction leading to a [2 ? 4] cycloadduct.

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Secondary α-deuterium kinetic isotope effects in [2+4] cycloaddition of (E)-2-phenylnitroethene to cyclopentadiene

Cited by 13 publications

References 20 publications

An experimental and theoretical study of the hetero Diels–Alder reactions between (E)-2-aryl-1-cyano-1-nitroethenes and ethyl vinyl ether: one-step or zwitterionic, two-step mechanism?

An experimental and theoretical study of the hetero Diels–Alder reactions between (E)-2-aryl-1-cyano-1-nitroethenes and ethyl vinyl ether: one-step or zwitterionic, two-step mechanism?

Understanding the Polar Character Trend in a Series of Diels-Alder Reactions Using Molecular Quantum Similarity and Chemical Reactivity Descriptors

A reexamination of the molecular mechanism of the Diels–Alder reaction between tetrafluoroethene and cyclopentadiene

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