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Related Concept Videos

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement01:24

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
Thermal Electrocyclic Reactions: Stereochemistry01:17

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Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Photochemical Electrocyclic Reactions: Stereochemistry01:26

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Woodward–Hoffmann Selection Rules and Microscopic Reversibility01:34

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Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
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A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
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Updated: Jun 26, 2026

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers
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Unveiling Electric Field-Driven Stereocontrol in Hurd-Claisen Rearrangements.

Mateus Rodrigues Barbosa1, Pedro H F Matias1, Daniel F Scalabrini Machado2

  • 1Laboratório de Estrutura Eletrônica e Dinâmica Molecular, Universidade Federal de Goiás, Goiânia, GO 74690-900, Brasil.

Journal of Chemical Theory and Computation
|June 25, 2026
PubMed
Summary
This summary is machine-generated.

External electric fields (EEFs) can control chemical reactions. This study shows that aligning EEFs with molecular dipoles reliably inverts stereoselectivity in the Hurd-Claisen rearrangement, enabling precise synthesis.

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Last Updated: Jun 26, 2026

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Area of Science:

  • Computational Chemistry
  • Organic Synthesis
  • Physical Chemistry

Background:

  • The Hurd-Claisen rearrangement is a key organic reaction.
  • Controlling stereochemistry in rearrangements is crucial for synthesis.
  • External electric fields (EEFs) offer a novel approach to influence reaction pathways.

Purpose of the Study:

  • To computationally investigate the effect of EEFs on the Hurd-Claisen rearrangement.
  • To understand how EEFs perturb dipole-field interactions and transition states.
  • To explore methods for enhancing EEF-mediated stereocontrol.

Main Methods:

  • High-level Density Functional Theory (DFT) calculations.
  • Systematic mapping of substituent effects on transition-state geometries.
  • Modeling gold-thiolate anchoring to amplify substrate polarization.
  • Analysis of oriented and nonoriented EEF effects using statistical ensembles.

Main Results:

  • Aligned EEFs significantly stabilize transition states, with molecular-axis alignment being most effective (>2 kcal·mol-1).
  • Gold-thiolate anchoring amplifies stabilization to over 20 kcal·mol-1.
  • Nonoriented fields can induce stereochemical bias via dipole torque (up to 2.5 kcal·mol-1).

Conclusions:

  • Dipole orientation is a quantitative predictor of EEF-mediated stereocontrol.
  • EEFs can serve as "invisible catalysts" for reagent-free synthesis.
  • Provides blueprints for deploying EEF control in various reactor platforms.