由远程性二醇诱导的酶选择性超分子催化
Piet W N M van Leeuwen1, David Rivillo, Matthieu Raynal
1Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain. pvanleeuwen@iciq.es
Journal of the American Chemical Society
|October 25, 2011
概括
这项研究引入了一种新的方法,用于合成使用高分子协调化合物的奇拉二氨酸库. 这些化合物有效地催化非对称化,在特定基质上达到高选择性 (ee),高达92%.
科学领域:
- 超分子化学 超分子化学
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- 性二素是不对称催化过程中至关重要的配体.
- 开发有效的方法来创建多样化的性二氨酸库对于催化剂的发现至关重要.
- 超分子化学为构建复杂的催化系统提供了一个多功能平台.
研究的目的:
- 介绍一种用于生成奇拉二芬库的新方法.
- 利用这些新型化合物作为在不对称化反应中的催化剂.
- 探索超分子结构和催化性能之间的关系.
主要方法:
- 通过 in situ 混合,合成涉及 (Ti), (Rh),阿奇拉尔二极管联体和奇拉尔二醇的高分子协调化合物.
- 这些化合物的应用作为催化剂在 (Z) - 甲基2-乙胺-3-烯酸盐的不对称化.
- 超分子结构和性诱导机制的表征.
主要成果:
- 成功合成了合双氨酸库.
- 触媒不对称化,以高达92%的酶选择活性 (ee) 实现.
- 证明,通过对性二醇与Ti的协调来引入性,在性中心和基质之间有显著的空间分离.
结论:
- 本文所介绍的 in situ 方法提供了一条有效的途径,以获得奇拉双氨酸库.
- 超分子催化剂在不对称化中表现出高效率和选择性.
- 超分子组合中的空间布局在控制立体选择性方面发挥着关键作用.
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.
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
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.
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.
Regioselectivity and Stereochemistry of Hydroboration
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
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...


