通过阳极生成的高价中间体进行电催化C-N合
Asim Maity1, Brandon L Frey1, Nathanael D Hoskinson1
1Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Journal of the American Chemical Society
|March 5, 2020
概括
这项研究引入了无金属高价电催化技术,以实现高效和可持续的有机合成. 超价中间体的阳极生成使新的C-H和N-H合反应成为可能,从而推进了合成电化学.
科学领域:
- 有机化学
- 电化学
- 可持续的合成
背景情况:
- 电合成化学为有机合成提供了可持续的途径.
- 超价化合物是有机转化中的多功能试剂.
研究的目的:
- 开发一种无金属的高价值电催化系统.
- 通过电化学实现高效的C-H/N-H合反应.
- 提供超值介导电化学的机械洞察力.
主要方法:
- 酸的阳极氧化产生高价中间体.
- 使用乙离子稳定短暂的中间体.
- 将开发的系统应用于分子内和分子间的C-N结合反应.
主要成果:
- 通过氧化C-H/N-H合证明了电子交界的有效合.
- 在分子内和分子间C-N键形成中展示了适用性.
- 通过乙离子稳定的一种过渡性I (II) 中间体.
结论:
- 这项工作介绍了首个无金属高价电催化剂的C-H功能化.
- 这些发现为合成电化学中超价介质的未来开发提供了机制理解.
- 这种方法提高了有机合成的效率和可持续性.
相关概念视频
Thermal and Photochemical Electrocyclic Reactions: Overview
2.9K
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.
2.9K
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
4.1K
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...
4.1K
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
7.3K
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
7.3K
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
2.3K
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
2.3K
Thermal Electrocyclic Reactions: Stereochemistry
2.4K
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.
2.4K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.8K
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.
8.8K


