(±) -communesin F的总合成通过循环添加与印度醇-2-one
Johannes Belmar1, Raymond L Funk
1Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA.
Journal of the American Chemical Society
|September 18, 2012
概括
研究人员在15个步骤中实现了 (±) -communesin F的总合成. 一个关键的循环添加反应迅速构建了天然产品的四环核,展示了一个高效的合成策略.
科学领域:
- 有机化学 有机化学
- 自然产品的合成自然产品的合成
背景情况:
- 社区F是一种复杂的天然产品,具有独特的四环结构.
- 有效的合成路径对于访问和研究这些分子至关重要.
研究的目的:
- 开发一个简洁而高效的 (±) -communesin F. 的总合成.
- 建立一个关键的循环加法步骤,用于构建核心结构.
主要方法:
- 总合成方法从4 - 基托醇开始.
- 使用了因多尔-2-和3 - - - - - - - - - - - - - - - - - - - - - - - - - - 乙酸乙烯) - - - - - - - - - - - - - - - - 的循环添加反应.
- 在合成中使用了15个线性步骤.
主要成果:
- 实现了15个步骤的 (±) -communesin F.的总合成.
- 获得了6.7%的整体收益率.
- 通过循环添加成功构建了含有aminal的下方四环核.
结论:
- 开发的合成提供了一个精简的路线到 (±) -communesin F.
- 关键的循环添加步骤是有效的,用于快速组装四环核.
- 这项工作为复杂的自然产品的合成方法做出了贡献.
相关概念视频
Cycloaddition Reactions: Overview
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.
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
[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.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
Conjugate Addition to α,β-Unsaturated Carbonyl Compounds
α,β-Unsaturated carbonyl compounds are molecules bearing a carbonyl and alkene functionality in conjugation with each other. The conjugation in the molecule leads to three resonance structures. The hybrid form exhibits two probable electrophilic sites: the carbonyl carbon and the β carbon.


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