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

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

10.4K
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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Conjugate Addition to α,β-Unsaturated Carbonyl Compounds01:09

Conjugate Addition to α,β-Unsaturated Carbonyl Compounds

4.4K
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.
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Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene01:17

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

6.0K
The electrophilic addition of hydrogen halides such as HBr to alkenes and nonconjugated dienes gives a single product as per Markovnikov’s rule.
6.0K
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry01:28

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

3.9K
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.
3.9K
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

2.6K
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
2.6K
Conjugate Addition (1,4-Addition) vs Direct Addition (1,2-Addition)01:27

Conjugate Addition (1,4-Addition) vs Direct Addition (1,2-Addition)

3.4K
α,β-Unsaturated carbonyl compounds with two electrophilic sites, the carbonyl carbon, and the β carbon, are susceptible to nucleophilic attack via two modes: conjugate or 1,4-addition and direct or 1,2-addition.
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are...
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  2. 銅 ((i) -触媒化された非対称結合 1,4-ダイエンの Β-置換アルケニルアザアレンへの添加
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  2. 銅 ((i) -触媒化された非対称結合 1,4-ダイエンの Β-置換アルケニルアザアレンへの添加

関連する実験動画

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

7.5K

銅 ((I) -触媒化された非対称結合 1,4-ダイエンの β-置換アルケニルアザアレンへの添加

Zhi-Zhou Pan1, Deng Pan2, Jia-Heng Li1

  • 1CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Centre for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Journal of the American Chemical Society
|January 9, 2023

PubMed で要約を見る

まとめ
この要約は機械生成です。

チラルアザレンの合成は,銅 ((I) -触媒結合添加によって達成される. この方法は,重要な医薬品の構成要素の高収量と優れたエナチオ選択性を提供します.

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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

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Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
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Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

Published on: May 26, 2019

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関連する実験動画

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
06:46

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
07:12

Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

Published on: July 17, 2020

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Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
07:50

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

Published on: May 26, 2019

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科学分野:

  • 有機化学
  • アシンメトリック・シンセシス
  • カタリシス

背景:

  • チラルアザレン化合物は多くの医薬品の重要な成分です.
  • これらの分子の効率的で選択的な合成方法を開発することは非常に重要です.

研究 の 目的:

  • 新しい銅 ((I) 触媒による非対称結合加法反応を開発する.
  • 高いステレオ選択性を持つアザリル基を持つキラル分子を合成する.

主な方法:

  • (E) -β置換アルケニルアザレネに1,4-ダイエンの非対称的結合添加を銅で触媒化した.
  • 高原子経済のために軽い陽子転送条件を利用した.
  • 選択性を理解するために,密度関数理論 (DFT) の計算を使用した.

主要な成果:

  • 中等から優れた収穫量と高いステレオ選択性 (drとenantioselectivity) を達成した.
  • さまざまなアザレンのヘテロサイクルを許容する幅広い基板範囲を示した.
  • (Z) -α,β-不飽和アザアレンと逆の絶対構成を観測した.

結論:

  • 開発された方法は,価値あるキラルアザレンの化合物への効率的な経路を提供します.
  • 反応の選択性は,C−C結合形成核愛性の加法ステップによって制御される.
  • 合成された製品は,さらなる化学的変換において合成的有用性を示す.