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Conjugate Addition of Enolates: Michael Addition01:08

Conjugate Addition of Enolates: Michael Addition

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The attack of a nucleophile at the β carbon of an α,β-unsaturated carbonyl compound is called conjugate addition. Conjugate addition reactions of active methylene compounds, such as β-diketones, β-keto esters, β-keto nitriles, and α-nitro ketones, are called Michael addition reactions.
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Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

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Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
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Conjugate Addition to α,β-Unsaturated Carbonyl Compounds01:09

Conjugate Addition to α,β-Unsaturated Carbonyl Compounds

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α,β-Unsaturated carbonyl compounds are molecules bearing a carbonyl and alkene functionality in conjugation with each other. The conjugation in the molecule leads to three resonance structures. The hybrid form exhibits two probable electrophilic sites: the carbonyl carbon and the β carbon.
4.6K
Nucleophilic Aromatic Substitution: Elimination–Addition01:11

Nucleophilic Aromatic Substitution: Elimination–Addition

4.2K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
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Electrophilic Addition to Alkynes: Hydrohalogenation02:35

Electrophilic Addition to Alkynes: Hydrohalogenation

10.4K
Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

3.8K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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Related Experiment Video

Updated: Sep 30, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Double Addition Reactions Involving Vinyl-Substituted N-Heterocycles and Active Methylene Compounds.

Jacob C Hood1, Yannick Tshikaya1, Aaren R Manz1

  • 1Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115, United States.

The Journal of Organic Chemistry
|March 10, 2022
PubMed
Summary

Researchers achieved double conjugate addition reactions using vinyl-substituted N-heterocycles and active methylene compounds. This method efficiently synthesizes dipyridyl and related heterocyclic products through acid catalysis.

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Area of Science:

  • Organic Chemistry
  • Heterocyclic Chemistry

Background:

  • N-heterocycles are crucial structural motifs in pharmaceuticals and materials science.
  • Conjugate addition reactions are fundamental transformations in organic synthesis.

Purpose of the Study:

  • To develop efficient methods for synthesizing dipyridyl and related heterocyclic compounds.
  • To explore the scope of double conjugate addition reactions with vinyl-substituted N-heterocycles.

Main Methods:

  • Acid-catalyzed conjugate addition reactions.
  • Utilizing active methylene compounds (1,3-dicarbonyls, cyano esters, cyano sulfones, malonyl nitrile) as nucleophiles.
  • Employing vinyl-substituted pyridines, quinoline, and pyrazine as Michael acceptors.

Main Results:

  • Successful double conjugate addition reactions were achieved.
  • A variety of dipyridyl and related heterocyclic products were synthesized.
  • The method demonstrated effectiveness with diverse nucleophiles and Michael acceptors, including 2,6-divinylpyridine.

Conclusions:

  • The developed method provides a facile route to complex heterocyclic structures.
  • This work expands the synthetic utility of conjugate addition reactions in heterocyclic chemistry.