Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Experiment Videos

Do secondary orbital interactions really exist?

J I García1, J A Mayoral, L Salvatella

  • 1Departamento de Química Orgánica, Instituto de Ciencia de Materiales de Aragón, Facultad de Ciencias, CSIC-Universidad de Zaragoza, E-50009 Zaragoza, Spain.

Accounts of Chemical Research
|October 21, 2000
PubMed
Summary

Revisiting classic examples of secondary orbital interactions (SOI) reveals no conclusive evidence for their role in Diels-Alder reactions. Alternative mechanisms like solvent effects and steric interactions better explain endo/exo selectivity.

Related Concept Videos

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Development and evaluation of the phenotypic 2G test to detect drug-resistant TB.

IJTLD open·2025
Same author

Brimonidine-LAPONITE® intravitreal formulation has an ocular hypotensive and neuroprotective effect throughout 6 months of follow-up in a glaucoma animal model.

Biomaterials science·2020
Same author

Spatial epidemiology for tuberculosis surveillance: a relevant add-on to routine surveillance.

The international journal of tuberculosis and lung disease : the official journal of the International Union against Tuberculosis and Lung Disease·2019
Same author

The issue of 'molecular radiators' in microwave-assisted reactions. Computational calculations on ring closing metathesis (RCM).

Organic & biomolecular chemistry·2014
Same author

Fatty acid derivatives and their use as CFPP additives in biodiesel.

Bioresource technology·2010
Same author

Pybox monolithic miniflow reactors for continuous asymmetric cyclopropanation reaction under conventional and supercritical conditions.

The Journal of organic chemistry·2007

Area of Science:

  • Organic Chemistry
  • Reaction Mechanisms
  • Computational Chemistry

Background:

  • Secondary orbital interactions (SOI) have been historically cited to explain stereoselectivity in pericyclic reactions.
  • The seminal work 'The Conservation of Orbital Symmetry' by Woodward and Hoffmann proposed key examples illustrating SOI.
  • Re-evaluation of these foundational examples is crucial for accurate mechanistic understanding.

Purpose of the Study:

  • To critically reassess the validity of commonly used examples demonstrating secondary orbital interactions (SOI).
  • To investigate alternative explanations for the observed endo/exo selectivity in Diels-Alder reactions.
  • To challenge the established mechanistic interpretations based on SOI.

Main Methods:

  • Re-examination of five historical examples of secondary orbital interactions (SOI) proposed by Woodward and Hoffmann.

Related Experiment Videos

  • Analysis of potential contributions from known chemical principles, including solvent effects, steric interactions, hydrogen bonding, and electrostatic forces.
  • Comparative evaluation of proposed SOI mechanisms against alternative explanations for Diels-Alder selectivity.

    • Main Results:

    • The analysis found no conclusive evidence supporting secondary orbital interactions (SOI) in the revisited examples.
    • Established mechanisms, such as solvent effects, steric hindrance, hydrogen bonds, and electrostatic forces, adequately explain the observed endo/exo selectivity.
    • The proposed SOI in classic cases appears to be an oversimplification or misinterpretation.

    Conclusions:

    • The typical illustrations of secondary orbital interactions (SOI) lack robust evidence.
    • Diels-Alder endo/exo selectivity can be effectively explained by a combination of well-understood, non-orbital factors.
    • A revision of mechanistic paradigms in pericyclic reactions may be warranted.