总合成的 (-) - - 迪克蒂奥斯塔丁
Gregory W O'Neil1, Andrew J Phillips
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
Journal of the American Chemical Society
|April 20, 2006
概括
这项研究详细介绍了一种新的Dictyostatin的融合总合成. 关键的方法包括介导循环和霍纳-瓦兹沃斯-埃蒙斯油性化,以获得高效的分子构造.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 自然产品的合成自然产品的合成
背景情况:
- 滴定是一种复杂的海洋天然产品,具有潜在的生物活性.
- 有效和可扩展的合成路径对于进一步的生物评估和模拟开发至关重要.
研究的目的:
- 为了描述一个新的融合总合成dictyostatin.
- 展示创新的合成方法来构建复杂的多基化天然产品.
主要方法:
- 收合成策略. 收合成策略.
- 介导的 (silyloxy) enynes的循环化,用于立体三合成.
- 使用olefin转化论的子单元合.
- 通过分子内霍纳-瓦兹沃斯-埃蒙斯油精化进行宏循环.
主要成果:
- 成功地构建了狄蒂奥斯塔丁的核心结构.
- 在复杂分子合成中证明介导循环和霍纳-瓦兹沃斯-埃蒙斯精的实用性.
- 在整个合成过程中实现了高立体化学控制.
结论:
- 描述的融合合成提供了一条有效的途径,以dictyostatin.
- 采用的合成策略适用于其他复杂的天然产品目标.
- 这项工作推动了总合成和天然产品化学领域的发展.
相关概念视频
Complexation Equilibria: Overview
Complexation reactions take place when dative or coordinate covalent bonds form between metal ions and ligands. The compounds formed in these reactions are called coordination compounds. The number of bonds formed between the metal ion and the ligands is called its coordination number. Generally, most metal ions in an aqueous solution are solvated by water molecules and thus exist as aqua complexes.
The equilibrium constant of the complexation reaction is represented as the formation constant...
The equilibrium constant of the complexation reaction is represented as the formation constant...
EDTA: Chemistry and Properties
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
EDTA: Conditional Formation Constant
Each EDTA molecule has six binding sites: four carboxyl groups and two amino groups. The fully protonated form of EDTA is represented as H6Y2+. However, it can exist in different forms, H5Y+, H4Y, H3Y−, H2Y2−, and HY3−, depending on the pH of the solution. In very basic solutions with pH > 10.17, the fully deprotonated form, Y4−, is the predominant species that readily complexes with metal ions in a 1:1 ratio.
For the equilibrium reaction of the metal with the Y4− form of EDTA, the formation...
For the equilibrium reaction of the metal with the Y4− form of EDTA, the formation...
EDTA: Auxiliary Complexing Reagents
EDTA titrations are usually carried out in highly basic conditions, where the fully deprotonated form of EDTA, Y4−, actively complexes with the free metal ions in the solution. Several metal ions precipitate as hydrous oxide (hydroxides, oxides, or oxyhydroxides) under these conditions, lowering the concentration of free metal ions in the solution. For this reason, auxiliary complexing agents or ligands such as ammonia, tartrate, citrate, or triethanolamine are used in EDTA titrations to...
EDTA: Direct, Back-, and Displacement Titration
The EDTA titration types for metal ion analysis include direct titration, back-titration, and replacement titration.
Direct titration involves buffering the metal ion solution to the desired pH and directly titrating with standard EDTA until the endpoint. The optimum pH ensures a large conditional formation constant of metal−EDTA and visibility of the free indicator color in the solution. In addition, auxiliary complexing reagents are used to prevent the precipitation of metal hydroxides and...
Direct titration involves buffering the metal ion solution to the desired pH and directly titrating with standard EDTA until the endpoint. The optimum pH ensures a large conditional formation constant of metal−EDTA and visibility of the free indicator color in the solution. In addition, auxiliary complexing reagents are used to prevent the precipitation of metal hydroxides and...
Complexometric EDTA Titration Curves
EDTA titration curves determine the free metal ion concentration. The titration curve represents the change in concentration of free metal ions (p function) as a function of the volume of EDTA added. This curve consists of three regions: before, at, and after equivalence points. Excess free metal ions are present before the equivalence point. Equal concentrations of metal ions and EDTA are present at the equivalence point. After the equivalence point, excess EDTA exists. This means slight...


