从正方形平面中消除β-的机制 (I) 氧化物复合物与可变的dative连接体
J Zhao1, H Hesslink, J F Hartwig
1Contribution from the Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8017, USA.
Journal of the American Chemical Society
|July 27, 2001
概括
这项研究表明,从醇复合物中消除β-是一种可逆的过程. 这一发现与以前的模型形成鲜明对比,并为有机金属反应途径提供了新的见解.
科学领域:
- 有机金属化学 有机金属化学
- 反应机制 反应机制
- 协调化学 协调化学
背景情况:
- 方形平面的alkoxo复合物,[Ir(CO) ((PPh3) 2 ((OR) ],表现出独特的稳定性和反应性.
- 了解β-消除对于催化和合成化学至关重要.
研究的目的:
- 阐明从醇复合物中消除β-的机制.
- 研究氨酸度和替代剂对反应途径的影响.
- 为了将观察到的机制与现有的氧化物和基消除模型进行比较.
主要方法:
- 机械学研究涉及运动分析,同位素效应和种族化实验.
- 在三素 (PPh3) 的存在下,醇复合物的热解.
- 改变氨酸度和溶剂以探测反应动力学.
主要成果:
- 发现β-排放是可逆的,速度常数受到β-碳替代物的最小影响.
- 对于氨酸度的反应顺序不同,表明复杂的动力学.
- 在1/k(obs) 与[PPh3]图的y截面上观察到一个主要的动态同位素效应.
结论:
- 一种涉及可逆β-消除的机制,其次是PPh3的关联性位移,解释了观察到的数据.
- 这种途径不同于拟议的直接消除,protic或双核机制.
- 氧化的消除可以通过类似于基复合物的途径进行,挑战先前的假设.
相关概念视频
Lewis Structures of Molecular Compounds and Polyatomic Ions
To draw Lewis structures for complicated molecules and molecular ions, it is helpful to follow a step-by-step procedure as outlined:
Newman Projections
Different notations are used to represent the three-dimensional structure of molecules on two-dimensional surfaces. One of the most commonly used representations is the dash-wedge formula. The dashed wedges, solid wedges, and the plane lines indicate the groups situated behind the plane, coming out of the plane, and in the plane, respectively.
The organic molecules rotate across the single bonds leading to numerous temporary three-dimensional structures of varying energy known as conformers.
The organic molecules rotate across the single bonds leading to numerous temporary three-dimensional structures of varying energy known as conformers.
Hydroboration-Oxidation of Alkenes
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
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.
Radical Formation: Homolysis
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
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...


