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Related Experiment Videos

1,3-Heterocumulene-to-alkyne

Fabian1, Krebs, Schonemann

  • 1Institut fur Organische Chemie, Universitat Hamburg, D-20146 Hamburg, Germany.

The Journal of Organic Chemistry
|January 10, 2001
PubMed
Summary
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This study calculates cycloaddition reactions of 1,3-heterocumulenes with acetylene and cycloalkynes. Computational methods reveal trends in activation energies and reaction energies, with experimental validation for carbon diselenide and isothiocyanates.

Area of Science:

  • Computational chemistry
  • Organic reaction mechanisms
  • Quantum chemistry

Background:

  • 1,3-heterocumulenes are versatile building blocks in organic synthesis.
  • Cycloaddition reactions are fundamental for forming cyclic compounds.
  • Understanding reaction energetics is crucial for predicting reactivity and outcomes.

Purpose of the Study:

  • To computationally investigate the transition structures and energy barriers of cycloaddition reactions involving 1,3-heterocumulenes and unsaturated systems.
  • To explore the influence of heteroatoms on the energetics of these cycloaddition reactions.
  • To compare theoretical predictions with experimental findings for validation.

Main Methods:

  • Ab initio quantum chemical methods (G2(MP2) and CBS-Q) were employed for calculations.

Related Experiment Videos

  • Density functional theory (DFT) and hybrid ONIOM methods were utilized for mechanistic studies.
  • Experimental studies corroborated the computational results.

    • Main Results:

    • Activation energies for homoheteroatomic cumulenes decrease in the order O > S > Se and NH > PH.
    • Reaction energies follow the order O > S ≈ Se and PH > NH.
    • Cycloaddition of carbon diselenide to cyclooctyne is faster than with carbon disulfide; 1:3 adducts form with isothiocyanates under specific conditions.

    Conclusions:

    • Computational methods accurately predict the relative reactivity and energetics of 1,3-heterocumulene cycloadditions.
    • The nature of the heteroatom significantly impacts reaction barriers and energy profiles.
    • Experimental validation confirms the theoretical models and provides insights into product formation pathways.