在olefin转化反应中-中间体的模型化合物
Donde R Anderson1, Daniel D Hickstein, Daniel J O'Leary
1Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
Journal of the American Chemical Society
|June 29, 2006
概括
研究人员开发了-烯复合体的模型系统,这对于烯转化论至关重要. 他们确定了两个侧结合的同质体,并使用NMR和X射线晶体学测量了它们的动态相互转换屏障.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 有机合成 有机合成
背景情况:
- 奥莱芬转化是有机合成中的重要反应.
- 了解催化转化酶的机制是开发新催化剂的关键.
- 鲁-烯复合体是这一机制中的重要中间体.
研究的目的:
- 为研究-烯复合体开发一个模型系统.
- 研究这些复杂的结构和动态.
- 为了深入了解氨酸转化酶的机制.
主要方法:
- 使用1,2-二维尼尔和一种前体,合成-烯酸添加物.
- 使用1H NMR光谱学对复合物的表征.
- 通过X射线晶体分析确定复杂结构.
- 使用光谱学测量动态互换屏障的测量.
主要成果:
- 形成了两种鲁-烯添加物,并被确定为侧结异构体.
- 发现氨酸和H2IMes连接体是相互协调的.
- 这两种异构体之间的动态相互转换具有19.1 +/- 0.1 kcal/mol的测量屏障.
结论:
- 开发的模型系统有效地允许研究-烯复合体.
- 这些发现提供了与氨酸转化机制相关的有价值的结构和动态信息.
- 这项研究有助于更深入地了解涉及的催化过程.
相关概念视频
Free-Radical Chain Reaction and Polymerization of Alkenes
The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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.
Olefin Metathesis Polymerization: Overview
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...


