通过C-N交叉合和C-H/C-H功能化,以电有机合成伊萨和水
Neetu Verma1, Rajdeep Tyagi2, Ashish Khanna3
1Department of Chemistry, IIT (Banaras Hindu University), Varanasi-221005, India. manisha.apc@itbhu.ac.in.
Organic & biomolecular chemistry
|August 11, 2023
概括
这项研究提出了使用的2 - 氨基乙的伊萨衍生物的高效电化学合成. 与传统的批量工艺相比,这种新的方法提供了更好的产量和更短的反应时间.
科学领域:
- 有机化学 有机化学
- 电化学 电化学 电化学
- 合成方法论 合成方法论
背景情况:
- 伊萨丁 (英多尔-2,3-) 和其衍生物是药物化学中的关键支架.
- 伊萨的现有合成途径可能是漫长而低收益的.
- 电化学方法为有机合成提供了可持续和高效的替代方案.
研究的目的:
- 开发一种高效和独特的电化学方法来合成异酸衍生物.
- 为了探索反应的范围,使用各种替代的2-氨基烯基底.
- 为了合成新的电化学活性异酸和酸.
主要方法:
- 使用I2-DMSO系统进行电化学合成.
- 在C-N交叉合和C-sp2-H/C-sp3-H功能化.
- 循环电压测量用于研究反应机制.
主要成果:
- 从各种替代的2 - 氨基烯基底物中获得了良好的至非常好的异氨酸衍生物产量.
- 与批量工艺相比,更短的反应时间和作为促进剂的显著提高了产量.
- 伊萨-化和乙芬-化成功合成,证明了该协议的多功能性.
结论:
- 开发的电化学方法提供了一个高效和独特的途径,以伊萨衍生物.
- 反应机制被证实是通过循环电压计进行扩散控制的.
- 这种方法为合成有价值的基于伊沙的化合物提供了更绿色和更有效的替代方案.
相关概念视频
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
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
Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction
3.4K
α-Substituted ketones or aldehydes can be synthesized from enamines by the Stork enamine reaction, named after its pioneer Gilbert Stork. Enamines are useful synthetic intermediates where the lone pair on nitrogen is in conjugation with the C=C bond. They resemble enolate ions, as the resonance forms of both species have a nucleophilic α carbon.
3.4K


![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)