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関連する概念動画

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.
2.2K
Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

2.9K
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.
2.9K
Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

1.9K
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
1.9K
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

2.5K
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.
2.5K
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.
3.8K
Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

2.1K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.1K

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関連する実験動画

Updated: Oct 7, 2025

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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理論とスペクトロスコピーを用いた光エノライゼーション駆動型サイクル添加の調節

Jiao Yu J Wang1, Mitchell T Blyth1, Michael S Sherburn1

  • 1Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 2601, Australia.

Journal of the American Chemical Society
|January 7, 2022
PubMed
まとめ

この研究は,計算および実験的方法を使用して,光エノ化/ダイエルス-アルダー (PEDA) 反応配列を調査する. PEDA配列は,カルボニルプロディエンの広範な適用性を示し,チオカルボニルとイミンは,ユニークな反応性課題と機会を提示する.

科学分野:

  • 有機光化学
  • コンピュータ化学
  • 反応メカニズムの研究

背景:

  • フォトエノライゼーション/ディエルス・アルダー反応 (PEDA) は強力な合成ツールである.
  • PEDA配列の範囲と限界を理解することは,その適用にとって極めて重要です.
  • 以前の研究では,PEDAの反応性に影響する要因を徹底的に調査していない.

研究 の 目的:

  • PEDA配列の幅広い調査を行う.
  • PEDA反応に対する様々な置換剤と反応パートナーの影響を調べる.
  • フォトエノライゼーション/ケレトロピク添加 (PECA) などの関連反応経路の可能性を調査する.

主な方法:

  • SMD溶解によるM06-2X/6-31+G (d,p) 計算を用いた.
  • 実験的な紫外線スペクトロスコーピーを用いて計算した結果です
  • 20個のプロディエンと20個のディエノフィルのテストセットを調査し,さまざまな電子的および構造的性質を有しました.

主要な成果:

  • PEDA配列は,カーボニル基プロディエンのほとんどの置換パターンに耐性がある.
  • チオカルボニル誘導体は,非効率なシステム間交差と競合する水素原子転送経路により,反応が遅い.

さらに関連する動画

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
11:44

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds

Published on: October 18, 2018

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Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals
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Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals

Published on: May 29, 2018

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関連する実験動画

Last Updated: Oct 7, 2025

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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Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
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Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds

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Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals
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Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals

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  • オーソアルキルイミンは興奮状態ではより高いバリアを示しますが,克服された場合,容易なPEDAを受けることができます.
  • ディエルス-アルダー反応の範囲は,以前に報告されたよりも広く,エチレンと電子豊富なアルケーンを含む反応の可能性があります.
  • 炭素一酸化物 (CO) は, [4+2]サイクル添加ではなく,容易 (4+1) チェレトロピク添加 (PECA) を受けると予測されています.

    • 結論:

    • PEDA配列は,特にカルボニルプロディエンの場合,広く適用可能な汎用反応である.
    • チオカルボニルおよびイミン系は,特定の条件下で利用できるユニークな反応性プロファイルを提供します.
    • 新しいフォトエノライゼーション/ケレトロピック添加 (PECA) 配列は,ベンザンネレートされたサイクロペンタノンのための金属フリー経路を提供します.