在Cu (I) -催化化酸环添加剂中,有双核铜中间体的直接证据
B T Worrell1, J A Malik, V V Fokin
1Department of Chemistry, The Scripps Research Institute, La Jolla, CA, USA.
概括
铜 (I) 催化化酸循环添加需要外部催化剂进行反应. 交叉实验揭示了循环加法过程中的逐步机制和相当的铜原子.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 反应机制 反应机制
背景情况:
- 铜 (I) 催化化酸循环添加对于合成复杂分子至关重要.
- 由于多个平衡和反应中间体,反应机制是复杂的.
研究的目的:
- 为了阐明铜 (I) 催化化酸循环添加的机制.
- 调查铜乙化物复合物和外源性催化剂的作用.
主要方法:
- 实时监测使用热流反应热度计.
- 使用同位素丰富的铜来源进行交叉实验.
主要成果:
- 单体铜乙化物复合物在没有添加催化剂的情况下对有机化物没有反应.
- 在循环添加过程中观察到逐步的碳键形成和相当的铜原子.
结论:
- 外源铜催化剂对于循环添加中铜乙化物复合物的反应性至关重要.
- 反应通过不同的步骤进行,涉及相应的铜原子.
相关概念视频
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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.
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.
Preparation of 1° Amines: Azide Synthesis
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the para position.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.


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