Conformer-specific polar cycloaddition of dibromobutadiene with trapped propene ions

@article{Kilaj2021ConformerspecificPC,
  title={Conformer-specific polar cycloaddition of dibromobutadiene with trapped propene ions},
  author={Ardita Kilaj and Jia Wang and Patrik Straň{\'a}k and Max Schwilk and Ux{\'i}a Rivero and Lei Xu and O. Anatole von Lilienfeld and Jochen K{\"u}pper and Stefan Willitsch},
  journal={Nature Communications},
  year={2021},
  volume={12}
}
Diels–Alder cycloadditions are efficient routes for the synthesis of cyclic organic compounds. There has been a long-standing discussion whether these reactions proceed via stepwise or concerted mechanisms. Here, we adopt an experimental approach to explore the mechanism of the model polar cycloaddition of 2,3-dibromo-1,3-butadiene with propene ions by probing its conformational specificities in the entrance channel under single-collision conditions in the gas phase. Combining a… 
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References

SHOWING 1-10 OF 79 REFERENCES

Reactive atomistic simulations of Diels-Alder-type reactions: conformational and dynamic effects in the polar cycloaddition of 2,3-dibromobutadiene radical ions with maleic anhydride

The kinetics, dynamics and conformational specificities for the ionic Diels-Alder reaction (polar cycloaddition) of maleic anhydride with 2,3-dibromobutadiene radical ions have been studied

AB INITIO STUDIES OF THE RADICAL CATION DIELS-ALDER REACTION

The radical cation Diels−Alder reaction of the 1,3-butadiene radical cation with ethylene, yielding the cyclohexene radical cation, was studied by B3LYP hybrid functional and QCISD(T)//QCISD

PATHWAYS FOR THE REACTION OF THE BUTADIENE RADICAL CATION, C4H6.+, WITH ETHYLENE

The Diels-Alder (DA) reaction, a [4+2] cycloaddition used to build six membered rings, is one of the most valuable cycloadditions in organic chemistry. In cases where the ene does not add to the

Quantum-chemistry-aided identification, synthesis and experimental validation of model systems for conformationally controlled reaction studies: separation of the conformers of 2,3-dibromobuta-1,3-diene in the gas phase.

This work presents an experimental approach that separates different diene conformers in a molecular beam as a prerequisite for the investigation of their individual cycloaddition reaction kinetics and dynamics under single-collision conditions in the gas phase.

Cycloaddition reactions between 1,3-butadiene radical cations and ethene in the gas phase

The reaction of [1,3-butadiene]+· with ethenc in the gas phase has been studied under low-pressure conditions. Experiments were conducted in a Fourier transform ion cyclotron resonance spectrometer

Reactive atomistic simulations of Diels-Alder reactions: The importance of molecular rotations.

Analysis of the minimum dynamic path indicates that rotational energy is crucial to drive the system toward the transition state in addition to collision energy, and the presence of bromine substituents in the diene accentuates the importance of rotational excitation to promote the reaction.

Stepwise Diels-Alder: more than just an oddity? A computational mechanistic study.

The results show that a conventional Diels-Alder transition state conformation yields intermediates in all four investigated cases, but that these are too short-lived to be detected experimentally for the less activated reactants, and that introduction of a hydrogen bond donating catalyst favors a stepwise pathway even for less activated dienophiles.

Mechanistic Aspects of Diels‐Alder Reactions: A Critical Survey

The question of concerted or consecutive bond formation arises in all types of cycloaddition reactions. Stereochemical investigations and studies of regiospecificity as well as intensive kinetic

Extraordinary Mechanism of the Diels-Alder Reaction: Investigation of Stereochemistry, Charge Transfer, Charge Polarization, and Biradicaloid Formation.

The Diels-Alder reaction between 1,3-butadiene and ethene is investigated from far-out in the entrance channel to the very last step in the exit channel thus passing two bifurcation points and extending the range of the reaction valley studied with URVA by 300% compared to previous studies.
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