通过对抗选择性单一化去对称化中环性胺基
Satoshi Takebayashi1, Jeremy M John, Steven H Bergens
1Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2.
Journal of the American Chemical Society
|August 26, 2010
概括
基拉尔循环胺基经过不对称的化,以使用催化剂产生具有高反选择性的酸乳酸. 这种脱对称反应有效地产生了多个立体中心,使复杂分子合成成为可能.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 不对称的合成方法
背景情况:
- 循环等离子体是药品中重要的结构图案.
- 在有机合成中,创建奇拉中心的高效方法至关重要.
研究的目的:
- 开发一种高分离选择性的方法,用于中环状物质的不对称化.
- 为了探索中环形模态的脱对称化,以产生多个立体中心.
主要方法:
- 不对称的化中环化伊米德使用转化[Ru (R) -BINAP (H) -R,R) -dpen) ]和相关的催化剂.
- 基中介反应在四基 (THF) 中.
- 随后的氧乳酸的功能化形成了离子和添加的印烯.
主要成果:
- 在将中环性胺基化成氧乳酸的单化过程中达到高的反选择性 (88-97% ee).
- 证明了高的反抗组和化学选择性.
- 在单个反应序列中成功创建了多达七个立体中心.
结论:
- 开发的催化系统提供了一条高效的途径,用于脱对称的中周期性物质.
- 这种方法允许对具有多个性中心的复杂分子进行立体选择性合成.
相关概念视频
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.
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.
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.
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.
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.


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