不对称的有机催化形式 [2 + 2] - 循环添加通过双功能H键指导二胺胺催化
Łukasz Albrecht1, Gustav Dickmeiss, Fabio Cruz Acosta
1Center for Catalysis, Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark.
Journal of the American Chemical Society
|January 28, 2012
概括
研究人员开发了一种新的有机催化方法,用于制造具有四个立体中心的循环butanes. 这种方法使用双激活和一种新的催化剂来精确控制循环添加反应.
科学领域:
- 机体催化剂是有机催化剂.
- 不对称的合成方法
- 循环添加反应的反应
背景情况:
- 有机催化剂为复杂分子合成提供了一种可持续的方法.
- 在循环butan建筑中实现高立体控制仍然是一个挑战.
- 双重激活策略可以提高反应性和选择性.
研究的目的:
- 提出一种新的有机催化概念,用于制造循环butanes.
- 为了在正式的 [2+2] - 循环加法中实现完全的二聚体和反聚体控制.
- 开发一种用于同时双重激活的新型双功能催化剂.
主要方法:
- 基于方胺的双功能氨基催化剂的设计和合成.
- 催化剂在α,β不和化物和酸之间进行正式的 [2+2] - 循环添加.
- 证明反应的潜力和范围.
- 计算研究以阐明立体化学结果.
主要成果:
- 成功构建了具有四个连续立体中心的循环butanes.
- 实现了完全的二聚体和反聚体控制.
- 展示了开发方法的广泛范围和潜力.
- 计算研究为反应机制和立体选择性提供了洞察力.
结论:
- 提出的有机催化概念使得高度立体控制的循环butanes的合成.
- 这种新型的双功能催化剂对于同时进行双重激活是有效的.
- 这种方法为不对称合成提供了一个强大的新工具.
相关概念视频
[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: 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.
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 Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
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...
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.


