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

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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.

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The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.

Aldol Condensation vs Claisen Condensation

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Aldol condensation is an acid or base-catalyzed condensation between aldehydes or ketones to give an α,ꞵ-unsaturated carbonyl compound. A base-promoted condensation between ester molecules to produce a ꞵ-ketoester is known as the Claisen condensation. In the presence of a base, both reactions involve deprotonation of the acidic α hydrogen to produce the corresponding enolates. The nucleophilic enolates attack their respective nonenolized carbonyl compound forming a tetrahedral...

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Regular Claisen condensation involves the synthesis of β-ketoesters by combining identical ester molecules bearing two α hydrogens in the presence of an alkoxide base. The reaction commences with the deprotonation of the acidic α hydrogen by the base to form a resonance stabilized ester enolate. This nucleophilic ion then attacks the carbonyl center of another ester molecule to generate a tetrahedral alkoxide intermediate. Next, the expulsion of the alkoxide group from the...

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Benzaldehyde, like formaldehyde, lacks an α hydrogen and cannot enolize to form an enolate. Hence, the reaction of benzaldehyde with a ketone in the presence of an aqueous base forms a single crossed product. This reaction is referred to as Claisen–Schmidt condensation.
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Updated: Jun 24, 2025

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

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Main Group-Catalyzed Cationic Claisen Rearrangements via Vinyl Carbocations.

Chloe G Williams¹, Sepand K Nistanaki¹, Krista Dong¹

¹Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.

Organic Letters

|June 6, 2024

Summary

A novel catalytic reaction efficiently forms sterically hindered carbon-carbon bonds using vinyl carbocations and allyl ethers. This method enables highly stereoselective synthesis of substituted vinyl ethers via a charge-accelerated Claisen rearrangement.

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Published on: September 8, 2013

Area of Science:

Organic Chemistry
Catalysis
Synthetic Methodology

Background:

Carbon-carbon bond formation is crucial in organic synthesis.
Developing efficient catalytic methods for constructing sterically hindered bonds remains a challenge.
Vinyl carbocations are reactive intermediates with potential for synthetic applications.

Purpose of the Study:

To report a new catalytic C-O coupling/Claisen cascade reaction.
To demonstrate the construction of sterically hindered C-C bonds.
To achieve highly stereoselective synthesis of substituted vinyl ethers.

Main Methods:

Utilizing borate salts as catalysts.
Employing vinyl carbocations intercepted by allyl ethers.
Conducting experimental and computational studies to elucidate the reaction mechanism.

Main Results:

Successful catalytic C-O coupling/Claisen cascade reaction.
Effective construction of sterically hindered C-C bonds.
Identification of a charge-accelerated [3,3] rearrangement mechanism.
Highly stereoselective synthesis of fully substituted vinyl ethers.

Conclusions:

The developed catalytic system provides an efficient route to sterically hindered C-C bonds.
The reaction proceeds via a novel charge-accelerated [3,3] rearrangement pathway.
This methodology offers a powerful tool for stereoselective synthesis in organic chemistry.