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

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

9.9K
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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Diels–Alder Reaction Forming Cyclic Products: Stereochemistry01:28

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

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The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
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Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry01:29

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

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Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
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Diels–Alder Reaction: Characteristics of Dienes01:29

Diels–Alder Reaction: Characteristics of Dienes

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The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is...
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Diels–Alder Reaction: Characteristics of Dienophiles01:24

Diels–Alder Reaction: Characteristics of Dienophiles

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In a Diels–Alder reaction, the diene is usually an electron-rich system and acts as a nucleophile, whereas the dienophile is electron-deficient and functions as an electrophile. Much like the diene, the nature of the dienophile significantly impacts the outcome of the reaction. 
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder...
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[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

2.6K
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.
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Updated: May 15, 2025

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones
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Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones

Published on: February 7, 2019

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極性ビスカリックス[4]ピロールオクタイミンケージへの含有によって媒介される二分子ダイエルス-アルダー反応

Jiaming Huang1, Pablo Ballester1,2

  • 1Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Avgda. Països Catalans 16, Tarragona 43007, Spain.

Journal of the American Chemical Society
|April 8, 2025
PubMed
まとめ

オクタイミンケージという新しい分子ボトルは,酵素活性を模倣して,反応物質を封じ込めることで,ディエルス・アルダー反応を加速します. この超分子化学的アプローチは反応速度と選択性を高めます

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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

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Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach
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Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach

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関連する実験動画

Last Updated: May 15, 2025

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones
10:17

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones

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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

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Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach
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Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach

Published on: June 10, 2021

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科学分野:

  • 超分子化学
  • 有機化学
  • 化学運動学

背景:

  • 酵素は特定の穴に基板を結合することで反応を加速する.
  • 人工的なシステムは 分子封じ込みで酵素の機能を真似ることができます
  • ディエルス・アルダー反応は 基本的な有機変異です

研究 の 目的:

  • 分子ボトルとして自己組み立てのオクタイミンケージを使用します.
  • このケージ内の二分子ダイエルス・アルダー反応の加速を 調べるためだ
  • 酵素機能を模倣する 檻の能力を調べるためだ

主な方法:

  • ダイナミックに自己組み立てたオクタアミンケージ合成
  • H 結合研究のためのNMRスペクトルタイトレーション
  • 熱力学分析のためのアイソテルミック・タイトレーション・カロリメトリー (ITC)
  • 構造特性を示すためにX線結晶学
  • ディエルス・アルダー反応の運動分析

主要な成果:

  • オクタイミンケージは反応物質を成功裏に結合し,三重複合体を形成する.
  • ~40Mの有効モラリティ (EM) を達成した.
  • 化学的バランスの変化が検出された.
  • 檻の狭い空間は 酵素の活性部位を模倣しています

結論:

  • ダイナミックに自己組み立てられたケージは 効果的な分子ボトルとして機能します
  • ケージ内のカプセル化により 二分子反応が著しく加速する.
  • この超分子アプローチは 人工酵素を設計するためのプラットフォームを提供します.