水性脉冲电化学通过一级联方法促进C-N键的形成
Meng He1, Yongmeng Wu2, Rui Li1
1Department of Chemistry, School of Science, Institute of Molecular Plus, Tianjin University, Tianjin, 300072, China.
Nature communications
|August 22, 2023
概括
这项研究提出了一种可持续的方法,利用脉冲电化学从酸盐和酸盐中制造阿里胺. 这种新的方法提高了C-N键形成的效率,并扩大了氨基合成的范围.
科学领域:
- 绿色化学 绿色化学
- 有机合成 有机合成
- 电化学 电化学 电化学
背景情况:
- 电催化C-N键的形成提供了一条可持续的途径,从废物中获得有机胺.
- 目前的方法面临反应范围的局限性,需要综合催化方法.
研究的目的:
- 开发一种新,高效和可持续的合成阿里胺的方法.
- 在单电化学介导反应中整合异质和均质的催化.
主要方法:
- 用水脉冲电化学来转化酸和酸.
- 在铜纳米珊瑚阴极上发生了酸盐电还原到氨的过程.
- 在现场生成的铜 (II) 催化了氨与酸在开关阳极电位下合的氨酸.
主要成果:
- 通过脉冲电化学协议实现了高利胺的产量.
- 该方法证明了广泛的基质范围,并促进了15N标记的阿里胺的合成.
- 脉冲协议抑制了副产品并加速了C-N键的形成.
结论:
- 开发的脉冲电化学方法为阿里胺合成提供了一个有前途和可持续的方法.
- 该方法可以扩展到其他反应,如循环加法和点击化学.
- 可回收的铜催化剂和高效的废物利用强调了该方法的绿色化学方面.
相关概念视频
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
3.2K
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
3.2K
Thermal and Photochemical Electrocyclic Reactions: Overview
2.4K
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.
2.4K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
2.8K
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...
2.8K
Thermal Electrocyclic Reactions: Stereochemistry
2.0K
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.
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.
2.0K
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
Selection Rules: Photochemical Activation
1.9K
Cycloaddition Reactions: Overview
2.6K
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.
2.6K


