通过 ((III) 基复合物的特皮里丁的脱氧化和功能化
Kimberly C Jantunen1, Brian L Scott, P Jeffrey Hay
1Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico, 87545, USA.
Journal of the American Chemical Society
|May 11, 2006
概括
与特皮里丁连接体的基复合物是不稳定的. 它们经历了基迁移,导致连接体脱体化和功能化,挑战了"无辜"特皮里丁连接体的想法.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 连接体设计 连接体设计
背景情况:
- 二连接物通常用于协调化学.
- 人们普遍认为,特皮里丁连接体的"无害"性质已经得到了广泛认可.
- 了解连接体的反应性对于催化剂的开发至关重要.
研究的目的:
- 为了研究 (III) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 和特皮里丁配合物复合物的稳定性.
- 探索这些复合体中的基团的反应性.
- 挑战了关于特皮里丁连接体行为的既定观点.
主要方法:
- 合成与2,2':6',2''-特皮里丁和4,4',4''-三-特特--2,2':6',2''-特皮里丁的 (III) -基复合物.
- 复合物的光谱和结构分析.
- 在环境条件下对反应路径的研究.
主要成果:
- (III) - 基复合物表现出不稳定性.
- 在环境条件下容易发生1,3-基迁移.
- 观察到特皮里迪尔连接体的dearomatization和ortho功能化.
结论:
- 氨酸连接体框架并不像以前所认为的那样"无辜".
- 基迁移是这些合物复合物的重要反应途径.
- 这些发现需要重新评估在有机金属化学中的特皮里丁连接体行为.
相关概念视频
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
Preparation of Diols and Pinacol Rearrangement
Compounds bearing two hydroxyl groups are known as diols. When the hydroxyl groups are located on adjacent carbon atoms, the diols are called vicinal diols or glycols. Under acidic conditions, vicinal diols undergo a specific reaction called pinacol rearrangement.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
[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.
Radical Formation: Elimination
Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions with respect to...
Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview
Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.
Aldol Condensation with β-Diesters: Knoevenagel Condensation
The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.


