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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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Nucleophilic Aromatic Substitution: Elimination–Addition01:11

Nucleophilic Aromatic Substitution: Elimination–Addition

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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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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

3.6K
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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[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction01:16

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

10.3K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
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Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

2.2K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene01:14

Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene

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Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
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Intramolecular Ynamide-Benzyne (3+2) Cycloadditions.

Tsukasa Tawatari1, Ritsuki Kato1, Riku Kudo1

  • 1Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan.

Angewandte Chemie (International Ed. in English)
|March 9, 2023
PubMed
Summary

This study details intramolecular (3+2) cycloaddition reactions using ynamides and benzyne. A novel method exploits chlorosilyl-functionalized benzyne precursors for efficient two-bond formation, revealing the dual reactivity of indolium ylides.

Keywords:
BenzyneCycloadditionHeterocyclesYlidesYnamides

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry
  • Cycloaddition Reactions

Background:

  • Intramolecular cycloaddition reactions are crucial for constructing complex molecular architectures.
  • Ynamides and benzyne are versatile building blocks in organic synthesis.
  • Controlling the reactivity of transient intermediates like ylides is a key challenge.

Purpose of the Study:

  • To develop a novel intramolecular (3+2) cycloaddition reaction between ynamides and benzyne.
  • To utilize benzyne precursors with a chlorosilyl group for efficient two-bond formation.
  • To investigate the ambivalent reactivity of the resulting indolium ylide intermediate.

Main Methods:

  • Intramolecular (3+2) cycloaddition reactions.
  • Use of ynamides as three-atom components.
  • Generation of benzyne from chlorosilyl-functionalized precursors.
  • Analysis of the intermediate indolium ylide's properties.

Main Results:

  • Successful intramolecular (3+2) cycloaddition between ynamides and benzyne was achieved.
  • Chlorosilyl groups on benzyne precursors facilitated efficient two-bond formation.
  • The indolium ylide intermediate demonstrated ambivalence, acting as both a nucleophile and electrophile at its C2 atom.

Conclusions:

  • A new synthetic route for intramolecular (3+2) cycloadditions involving ynamides and benzyne has been established.
  • The developed method offers a powerful tool for accessing complex heterocyclic structures.
  • The study elucidates the dual nucleophilic and electrophilic nature of indolium ylides, expanding their synthetic utility.