不对称的 (+) -阿尔斯拉辛A的总合成
Jun-Jun Yao1, Rui Ding1, Xiaoming Chen1,2
1The State Key Laboratory of Chemical Oncogenomics, Guangdong Provincial Key Laboratory of Nano-Micro Materials Research, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University, Shenzhen 518055, China.
Journal of the American Chemical Society
|July 27, 2022
概括
科学家们首次实现了 (+) - 阿尔斯拉辛A的不对称总合成. 关键步骤包括不对称的基化,氧化-循环添加和中断的皮克特-斯格勒反应来构建复杂分子.
科学领域:
- 有机化学
- 合成化学
- 医学化学
背景情况:
- 阿尔斯拉辛A是一种复杂的天然产物,具有独特的多环结构.
- 对药物发现和化学生物学来说,开发高效的合成途径至关重要.
研究的目的:
- 实现 (+) - 阿尔斯顿拉辛A的第一个不对称的总合成.
- 开发新的合成方法来构建复杂的分子架构.
主要方法:
- 催化不对称的基化以建立C15立体中心.
- 内分子氧化- [3 + 2] 循环添加 (INOC [3 + 2]) 用于循环[b]骨架构和C20四级中心安装.
- 晚期中断的皮克特-斯勒反应 (IPSR) 用于快速组装核心结构.
主要成果:
- 首次成功完成 (+) - 阿尔斯顿拉辛A的非对称总合成.
- 在复杂分子合成中展示Pd催化基化,INOC [3 + 2]和IPSR的新应用.
- 建立关键的立体中心,包括一个具有挑战性的全碳四级中心.
结论:
- 开发的合成策略提供了一个有效的 (+) -阿尔斯拉辛A的途径.
- 使用的方法为合成其他复杂的天然产品和候选药物提供了有价值的工具.
- 这种合成促进了非对称合成和自然产品化学领域的发展.
相关概念视频
Preparation of Alcohols via Substitution Reactions
6.1K
Overview
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
6.1K
Preparation of Alkynes: Alkylation Reaction
10.5K
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
10.5K
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
3.6K
Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.
3.6K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.7K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
10.7K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.4K
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...
3.4K
Sharpless Epoxidation
4.2K
The conversion of allylic alcohols into epoxides using the chiral catalyst was discovered by K. Barry Sharpless and is known as Sharpless epoxidation. The use of a chiral catalyst enables the formation of one enantiomer of the product in excess. This chiral catalyst is mainly a chiral complex of titanium tetraisopropoxide and tartrate ester (specific stereoisomer). The stereoisomer used in the chiral catalyst dictates the formation of the enantiomer of the product. In other words, the use of...
4.2K


