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Related Experiment Videos

Dichlorocarbene addition to cyclopropenes: a computational study.

Dina C Merrer1, Paul R Rablen

  • 1Department of Chemistry, Barnard College, 3009 Broadway, New York, New York 10027, USA. dmerrer@barnard.edu

The Journal of Organic Chemistry
|February 26, 2005
PubMed
Summary

Dichlorocarbene addition to cyclopropenes occurs via a non-least-motion pathway, with low energy barriers. Reaction dynamics, not intermediates, control product distribution in both gas and solution phases.

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Area of Science:

  • Organic Chemistry
  • Computational Chemistry
  • Reaction Mechanism Studies

Background:

  • Cyclopropenes are strained cyclic alkenes with unique reactivity.
  • Dichlorocarbene (:CCl2) is a reactive intermediate used in cycloaddition reactions.
  • Understanding reaction pathways is crucial for predicting product formation.

Purpose of the Study:

  • To investigate the reaction mechanism of dichlorocarbene addition to 1,2-disubstituted cyclopropenes.
  • To determine the influence of phase (gas vs. solution) on the reaction pathway.
  • To elucidate the factors controlling product distribution.

Main Methods:

  • Hybrid density functional theory (B3LYP/6-31G) calculations were employed.
  • Calculations were performed in both the gas phase and using a continuum solvation model (acetonitrile).

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  • Potential energy surfaces were analyzed to identify reaction paths and intermediates.

    • Main Results:

    • The addition follows an asymmetric, non-least-motion approach in both phases.
    • Energy barriers for addition are low, ranging from 0 to 2 kcal/mol.
    • The reaction proceeds concertedly, yielding either 1,3-dienes or bicyclobutanes.
    • A bifurcating pathway suggests reaction dynamics control product distribution.
    • No stable dipolar intermediate was found on the potential energy surface.

    Conclusions:

    • Dichlorocarbene addition to cyclopropenes is a concerted process.
    • Reaction dynamics play a critical role in determining the product outcome.
    • The absence of a dipolar intermediate simplifies the mechanistic understanding.