关于 (±) -Gelsemoxonine的总合成方法
Stefan Diethelm1, Erick M Carreira
1Eidgenössische Technische Hochschule Zürich, HCI H335, 8093 Zürich, Switzerland.
Journal of the American Chemical Society
|May 22, 2013
概括
成功实现了Gelsemoxonine的总合成,这是一个Gelsemium类化合物. 关键步骤包括一种新的环收缩和二聚体选择性减小赫克循环,以构建其独特的结构.
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
- 药用化学 医学化学
背景情况:
- 凝素是Gelsemium的类化合物,具有复杂的结构,具有不寻常的亚齐丁丁环.
- 复杂的自然产品的合成对于理解它们的生物活性和开发新的治疗剂至关重要.
研究的目的:
- 为了实现Gelsemoxonine的第一个完全合成.
- 开发适用于复杂类结构的新型合成方法.
主要方法:
- 一个新的环收缩的螺旋cyclopropane isoxazolidine产生一个关键的β-lactam中间体.
- 将β-乳酸制成Gelsemoxonine的阿兹提丁核心.
- 高度二分体选择性还原性赫克循环化用于氧醇环系统的构建.
- 基因的定向水化,以安装乙基基部分.
主要成果:
- 成功和高效的Gelsemoxonine的总合成.
- 展示了一种新的螺旋cyclopropane isoxazolidine环收缩策略.
- 在天然产品合成中应用高度二分体选择性的减少式赫克循环.
- 建立针对安装的定向水化方法.
结论:
- 开发的合成途径为Gelsemoxonine和相关的Gelsemium类化合物提供了一条可行的途径.
- 采用的新方法对合成其他含的复杂异环有价值.
- 这种合成为进一步对Gelsemoxonine及其类似物进行生物评估奠定了基础.
相关概念视频
01:14Alkylation of β-Diester Enolates: Malonic Ester Synthesis
Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.
03:00Preparation of Epoxides
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...