协调化学 umpolung:在氨酸易斯接受器上的一个氨酸连接体
Neil Burford1, Paul J Ragogna, Katherine N Robertson
1Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada.
Journal of the American Chemical Society
|January 17, 2002
概括
一个盐和一个氨基-氨基-氨基类盐之间的反应形成了一个新的复合体. 这项研究详细介绍了第一个易斯基复合物在素易斯酸上.
科学领域:
- 有机金属化学 有机金属化学
- 无机化学 无机化学 有机化学
背景情况:
- 素易斯酸在催化和合成中至关重要.
- 化合物表现出不同的反应性和协调化学.
研究的目的:
- 为了合成和描述一个新型的复合体,其中包括一个易斯基与素易斯酸协调.
- 为了研究氨基-伊米诺加伦与盐的反应性.
主要方法:
- 五甲菲诺三甲硫酸盐与氨基-氨基氨基的反应.
- 由此产生的复合物的光谱表征 (例如,NMR,IR).
- 进行X射线晶体学以确定固态结构.
主要成果:
- 实现了三 (Ph3P) 的定量替代.
- 在氨酸易斯酸上形成易斯基的第一个特征复合物.
- 该结构揭示了和素之间独特的协调模式.
结论:
- 这项工作扩大了易斯酸-易斯基引证的范围.
- 新型 - 素复合物为新的催化应用开辟了道路.
- 合成路线提供了一种可靠的方法来访问这些独特的结构.
相关概念视频
Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview
The Fischer esterification reaction was developed by the German chemist Emil Fischer in 1895. It is a condensation reaction between carboxylic acids and alcohols in an acidic medium to give esters and water.
Acid Halides to Esters: Alcoholysis
Alcoholysis is a nucleophilic acyl substitution reaction in which an alcohol functions as a nucleophile. Acid halides react with alcohol to produce esters. The mechanism proceeds in three steps:
Amines to Alkenes: Hofmann Elimination
Alkenes can be obtained from amines via an E2 elimination. The amine is first converted into a good leaving group, such as a quaternary ammonium salt. This is accomplished by treating the amine with an excess of alkyl halide, which results in a halide salt. Next, the halide salt is transformed into a hydroxide salt that functions as a base to enable elimination.
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
α-Hydroxy Ketones via Reductive Coupling of Esters: Acyloin Condensation Overview
The pinacol and McMurry reactions involve the reductive coupling of ketones or aldehydes. Similarly, the bimolecular reductive coupling of two ester molecules in the presence of sodium metal in an aprotic solvent yields an α-hydroxy ketone product. The α-hydroxy ketone is also called acyloin, so the reaction is referred to as ‘acyloin condensation.’
Acid-Catalyzed Aldol Addition Reaction
The aldol reaction of a ketone under acidic conditions successfully forms an unsaturated carbonyl as the final product instead of an aldol. The acid-catalyzed aldol reaction is depicted in Figure 1.
Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism
Carboxylic acids react with alcohols to yield esters via an acid-catalyzed condensation reaction called Fischer esterification. This is a nucleophilic acyl substitution reaction that proceeds via a tetrahedral intermediate, where a water molecule is eliminated as the leaving group.


