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Acid-Catalyzed α-Halogenation of Aldehydes and Ketones01:21

Acid-Catalyzed α-Halogenation of Aldehydes and Ketones

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By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
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Ketones with Nonenolizable Aromatic Aldehydes: Claisen–Schmidt Condensation01:01

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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.
As the self-condensation of ketones is generally not favored in basic conditions, the self-condensed products do not form in the reaction between ketones and benzaldehyde. The general reaction of Claisen–Schmidt...
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[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement01:24

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

2.1K
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.
2.1K
Esters to β-Ketoesters: Claisen Condensation Mechanism01:08

Esters to β-Ketoesters: Claisen Condensation Mechanism

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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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Ethers are generally unreactive and unsuitable for direct nucleophilic substitution reactions since the alkoxy groups are strong bases and, therefore, poor leaving groups. However, ethers readily undergo acidic-cleavage reactions. Ethers can be converted to alkyl halides when heated with strong acids such as HBr and HI in a sequence of two substitution reactions.
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Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives01:18

Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives

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Aldehydes are more reactive than carboxylic acids and hence, can get over-reduced to alcohol in the presence of strong reducing agents. Therefore, carboxylic acids are inefficient in preparing aldehydes using LAH.
Carboxylic acid derivatives like acid chlorides and esters are more easily reducible than the corresponding acids. The derivatives reduce in the presence of mild reducing agents to give aldehydes. Aldehydes can also be prepared by Rosenmund reduction, that is, the reduction of...
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Aliphatic Ketone Claisen Rearrangement: Troubleshooting the Transetherification Step by Identifying a Stable Acid

Veera K Bruce1, Kaveh Farshadfar2, Aino Rolig1

  • 1Department of Chemistry and NanoScience Center, University of Jyväskylä, P.O. Box 35, FI-40014, Jyväskylä, Finland.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|July 20, 2024
PubMed
Summary

A novel catalytic method efficiently converts allylic alcohols into unsaturated ketones using 4-chlorobenzoic acid. This metal-free process is versatile, tolerating various substrates and protecting groups.

Keywords:
Acid catalysisClaisen rearrangementReaction optimization

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Area of Science:

  • Organic Chemistry
  • Catalysis

Background:

  • The Claisen rearrangement is a fundamental carbon-carbon bond-forming reaction.
  • Developing efficient and metal-free catalytic protocols is crucial for sustainable synthesis.

Purpose of the Study:

  • To develop an optimized, metal-free catalytic protocol for the aliphatic ketone Claisen rearrangement.
  • To identify an optimal catalyst for the efficient conversion of allylic alcohols to γ,δ-unsaturated ketones.

Main Methods:

  • Optimization of reaction conditions to identify the best catalyst.
  • Utilizing 4-chlorobenzoic acid as the optimal catalyst.
  • Employing a one-pot reaction strategy.
  • Conducting density functional theory (DFT) studies to understand the reaction mechanism.

Main Results:

  • 4-chlorobenzoic acid was identified as the optimal catalyst for the aliphatic ketone Claisen rearrangement.
  • A one-pot, metal-free catalytic protocol was established for the synthesis of γ,δ-unsaturated ketones from allylic alcohols.
  • The protocol demonstrated tolerance towards various substrates, including those with acid-labile protecting groups.
  • DFT studies and reaction monitoring indicated that the final rearrangement step possesses the highest activation barrier.

Conclusions:

  • The developed protocol offers an efficient and versatile method for synthesizing γ,δ-unsaturated ketones.
  • The use of 4-chlorobenzoic acid provides a sustainable, metal-free alternative for Claisen rearrangements.
  • Understanding the activation barrier of the rearrangement step can guide further optimization efforts.