电化学启用自然产品的总合成
Chad E Hatch1, William J Chain2
1Chemical Biology, Memorial Sloan Kettering Cancer Center, 417 E. 68 St., New York, NY, 10065 (United States).
ChemElectroChem
|December 18, 2023
概括
电化学方法使得天然产品合成的新型碳-碳键形成成为可能. 这篇综述强调了不同的合成策略和机制性见解,扩大了化学家的能力.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 电化学 电化学 电化学
背景情况:
- 电化学技术在有机合成中有着悠久的历史,可以追溯到1800年代.
- 电化学领域为化学家提供了一个不断扩大的工具包.
- 自然产品合成是电化学方法越来越多地应用的一个关键领域.
研究的目的:
- 为通过电化学技术实现的天然产品总合成提供视角.
- 专注于骨架组装中的电化学碳-碳键形成.
- 讨论机械细节,并提供这些债券形成的代表性例子.
主要方法:
- 关于使用电化学方法进行天然产品总合成的文献综述.
- 对电化学碳-碳键形成的分析.
- 讨论机械路径,并与传统合成方法进行比较.
主要成果:
- 电化学技术促进了独特的碳-碳键形成,这对于组装自然产品骨架至关重要.
- 这些方法提供了与传统化学方法不同的途径.
- 该综述展示了通过电化学实现的自然产品成功合成的各种例子.
结论:
- 电化学合成为自然产品组装的传统方法提供了补充策略.
- 越来越多的电化学工具集为天然产品合成提供了新的视角和可能性.
- 了解这些反应的机制细节是它们更广泛应用的关键.
相关概念视频
Thermal and Photochemical Electrocyclic Reactions: Overview
2.3K
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.
2.3K
Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
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
1.8K
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 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
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.3K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.3K
Pericyclic Reactions: Introduction
8.3K
Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
8.3K

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