通过互补的双螺旋形态形成的灾难选择性 imine 键的形成
Hidekazu Yamada1, Yoshio Furusho, Eiji Yashima
1Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan.
Journal of the American Chemical Society
|April 18, 2012
概括
状胺基模板指导从状单体中二重螺旋胺基键的二重选择性形成. 这种模板策略控制了由此产生的种族胺的立体化学,影响了反应速率和选择性.
科学领域:
- 超分子化学 超分子化学
- 有机合成 有机合成
- 立体化学是一种立体化学.
背景情况:
- 状模板对于控制立体选择性反应至关重要.
- 阿米丁二次体为构建复杂分子架构提供了一个多功能平台.
- 胺基键的形成是有机化学的一个基本反应.
研究的目的:
- 为了合成光学活跃的阿米丁二元链作为模板.
- 为了研究它们在二分体选择性 imine-bond形成中的应用.
- 了解模板结构对立体化学结果的影响.
主要方法:
- 合成带有多种链接器的 chiral 和 achiral amidine 双质链.
- 通过使用阿基拉尔碳酸单体和种族性1,2-环二氨酸,进行二重选择性胺基形成.
- 使用核磁共振 (NMR) 光谱学进行表征.
- 动力学研究以阐明反应机制.
主要成果:
- 阿米丁二次模板成功地指导了偏好双手双螺旋体的二重选择性形成.
- 模板性和链接器刚性显著影响了种族氨基的二元选择性.
- 胺基键形成通过两步可逆机制进行,第二步是速率决定和螺旋形成.
结论:
- 光学活跃的阿米丁二次体作为有效的合模板,用于二分 stereoselective imine 合成.
- 模板的超分子结构决定了产品的立体化学偏好.
- 这项工作提供了对模板控制合成和螺旋自组装机制的见解.
相关概念视频
Aldehydes and Ketones with Amines: Imine Formation Mechanism
Imine formation involves the addition of carbonyl compounds to a primary amine. It begins with the generation of carbinolamine through a series of steps involving an initial nucleophilic attack and then several proton transfer reactions. The second part includes the elimination of water, as a leaving group, to give the imine.
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
Imines are formed under mildly acidic conditions. A pH of 4.5 is ideal for the reaction.
If the pH is low or the solution is too acidic, the reaction slows down in the...
Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview
Primary amines react with carbonyl compounds—aldehydes and ketones—to generate imines. Imines consist of a C=N double bond and are named Schiff bases after its discoverer—the German chemist Hugo Schiff. On the other hand, secondary amines react with carbonyl compounds to give enamines. In enamines, the presence of a C=C double bond adjacent to the nitrogen atom leads to the delocalization of the lone pair.
Aldehydes and Ketones with Amines: Enamine Formation Mechanism
Enamine formation involves the addition of carbonyl compounds to a secondary amine through a series of reactions. The mechanism begins with the generation of carbinolamine, a nucleophilic attack followed by several proton transfer reactions. The hydroxyl group of the carbinolamine is converted into water to make a better leaving group that can push the reaction forward by eliminating a water molecule. In enamine formation, the last step involves the abstraction of a proton from the α carbon to...
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.
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.
Stereoisomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...


