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関連する概念動画

Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

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.
Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

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.
Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

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

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

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.
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation

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関連する実験動画

Updated: Jun 17, 2026

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of &#945;-Imino &#947;-Lactones and Alkylidene Pyrazolones
10:17

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

Published on: February 7, 2019

二重 [3 + 2] フォトサイクロアディション反応.

Clive S Penkett1, Jason A Woolford, Iain J Day

  • 1Department of Chemistry and Biochemistry, University of Sussex, Brighton BN1 9QJ, UK. c.s.penkett@sussex.ac.uk

Journal of the American Chemical Society
|December 17, 2009
PubMed
まとめ

新しい二重 [3 + 2] フォトサイクロアディション反応により,複雑な窓構造が1つのステップで作られます. この効率的な合成により,複数のリングとステレオセンターが形成され,有機合成の方法論が進歩しました.

科学分野:

  • 有機化学 オーガニック・ケミストリー
  • フォトケミストリー フォトケミストリー
  • 合成方法論 合成方法論

背景:

  • フォトサイクロアディション反応は,複雑な分子構造の構築に不可欠です.
  • Fenestranesは,緊張リングシステムを持つポリサイクリック化合物のユニークなクラスを表しています.
  • 窓への効率的な合成経路の開発は,有機化学における重要な課題です.

研究 の 目的:

  • フェネストラン合成のための新しい二重 [3 + 2] フォトサイクロアディション反応を報告する.
  • 単一の合成操作で複数の炭素-炭素結合,環,ステレオセンターの形成を実証する.
  • フォトサイクロアディションおよびその後の光反応のメカニズム的経路を探求する.

主な方法:

  • アロマティックアセタルを原材料として利用した光化学反応.
  • 構造の解明のための光譜分析 (NMR,質量スペクトロメトリー).
  • 反応中間物質の分離と特徴づけを含むメカニズム研究.

主要な成果:

  • 驚くべき二重 [3 + 2] フォトサイクロアディション反応により,芳香性アセタル1からフェネストラン2を成功して合成した.
  • ワンポットプロセスは,4つの新しい炭素-炭素結合,5つの新しいリング,7つの新しいステレオセンターを生成しました.

さらに関連する動画

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

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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

関連する実験動画

Last Updated: Jun 17, 2026

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of &#945;-Imino &#947;-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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[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
09:12

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

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

  • 線形メタフォトサイクロドクト3からの連続反応経路が観察され,角形メタフォトサイクロドクト4の代替断片転位フォト反応と共にトライサイクル6を生成した.

    • 結論:

    • 報告された光サイクロアディション反応は,複雑なフェネストラン誘導体への効率的でステレオ選択的な経路を提供します.
    • この方法論は,高度な原子とステップエコノミーで複雑なポリサイクルフレームワークを構築するための強力なツールを提供します.
    • 競合する反応経路を理解することで,光化学的変換の制御と予測性が向上します.