可见光诱导的双重基催化回循环/自我促进的 [2+2] 分子间循环添加
Xiaogang Tong1, Linlin Ren1, Yonggong Wang1
1Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Key Laboratory of Research and Development of Natural Products, School of Pharmacy, Yunnan University, Kunming 650500, China.
Organic letters
|March 12, 2025
概括
可见光催化使新的化学反应通过加速在赫克循环中消除抗β-化物. 还发现了一种涉及 [2+2] 光环添加的新型并列反应,没有额外的光催化剂.
科学领域:
- 有机化学 有机化学
- 光催化作用的光催化
- 有机金属化学 有机金属化学
背景情况:
- 可见光光催化剂为化学合成提供了一种可持续的方法.
- 复合物越来越多地被用作光催化剂,主要是通过Ni (II) 同解或化激活.
- 对于赫克循环和 [2+2] 光环添加的现有方法通常需要特定的光催化剂或恶劣的条件.
研究的目的:
- 探索光刺激物种在有机转化中的新型应用.
- 研究光催化剂影响赫克循环的机制.
- 发现可见光光催化剂促进的新联反应.
主要方法:
- 使用可见光照射与催化剂一起使用.
- 在赫克循环反应中研究抗β-化物消除的加速.
- 描述一个涉及分子间 [2+2] 光环添加的双重反应.
主要成果:
- 发现光激物种可以加速Heck循环化中的抗β-化物消除步骤.
- 开发了一种新的双重反应,将赫克循环与基质自我促进的分子间 [2+2] 光环添加相结合.
- 这种双重反应有效地进行,不需要额外的光催化剂.
结论:
- 可见光催化为促进具有挑战性的有机转化提供了一个强大的平台.
- 通过光激发加速抗β-化物消除的加速,开辟了Heck循环化中的新途径.
- 发现的双重反应突显了在可见光下开发高效,无催化剂的过程的潜力.
相关概念视频
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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.
[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.
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
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 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.
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