由联结驱动的拓化学转化反应
Kana M Sureshan1, Tomohiro Murakami, Tomomi Miyasou
1Department of Applied Chemistry, Faculty of Engineering, Ehime University, Matsuyama 790-0607, Japan. sureshankm@yahoo.co.in
Journal of the American Chemical Society
|July 30, 2004
概括
一个固态热反应意外地将一个myo-inositol衍生物转化为另一个. 这种由晶体结构和结合驱动的拓化学转基因化,为固态化学提供了新的见解.
科学领域:
- 固态化学 固态化学
- 有机化学 有机化学
- 晶体学 晶体学是指结晶学.
背景情况:
- 肌氨基醇衍生物是重要的碳水化合物,具有多种应用.
- 了解固态反应对于材料科学和合成至关重要.
- 保护是碳水化合物化学中常见的一种策略.
研究的目的:
- 为了研究一种异常的热异构反应的myo-inositol衍生物.
- 阐明观察到的固态反应背后的机制和驱动力.
- 报告第一个托波化学转化反应的实例.
主要方法:
- 单晶X射线衍射以确定分子和晶体结构.
- 固态热分析以研究异构化过程.
- 计算建模以了解反应路径和过渡状态 (如果适用,尽管在抽象中没有明确说明).
主要成果:
- 观察到1,2;3,4-di-O-isopropylidene-myo-inositol到1,2;5,6-di-O-isopropylidene-myo-inositol在固态中的一个意想不到的热异构.
- 确定反应是以拓化学驱动的,这意味着它是由晶格中的分子排列控制的.
- 确定了强大的分子间结作为一个关键因素,预先组织了移动的分子.
结论:
- 观察到的异构化是一种新型的拓化学转基因化反应.
- 晶格中的分子间键通过将反应组靠近来促进反应.
- 晶体包装决定了反应路径,强调了固态结构在化学转换中的重要性.
相关概念视频
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Aldehydes and Ketones with Alcohols: Hemiacetal Formation
Similar to water, alcohols can add to the carbonyl carbon of the aldehydes and ketones. The addition of one molecule of alcohol to the carbonyl compound forms the hemiacetal or half acetal. As depicted below, in a hemiacetal, the carbon is directly linked to an OH and OR group.
Thermal and Photochemical Electrocyclic Reactions: Overview
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.
Keto–Enol Tautomerism: Mechanism
The keto and enol forms are known as tautomers and they constantly interconvert (or tautomerize) between the two forms under acid or base catalyzed conditions. Both the reactions involve the same steps—protonation and deprotonation— although in the reverse order.


