烯分子的区域选择性循环添加反应与Si上的不对称二元{100) c{4 x 2}
Kazuhiro Oguchi1, Masashi Nagao, Hirobumi Umeyama
1Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa-city, Chiba 277-8581, Japan.
Journal of the American Chemical Society
|February 1, 2007
概括
研究人员研究了表面的基反应. 他们发现,马尔科夫尼科夫.
科学领域:
- 表面科学是一门学科.
- 材料化学 材料化学
- 有机化学 有机化学
背景情况:
- 100) c) 4 x 2) 表面由于其不对称的二元结构,具有独特的反应性.
- 了解基吸附对于开发基于的新材料和催化剂至关重要.
研究的目的:
- 为了研究二甲基和在Si100 (c) 4 x 2表面上的吸附状态和反应途径.
- 阐明控制非对称基和Si100 (c) 4 x 2表面之间的循环添加反应区域选择性的因素.
主要方法:
- 使用低温扫描道显微镜 (LT-STM) 可视化吸附结构.
- 使用第一原理计算来了解反应机制和电子性质.
主要成果:
- 在非对称基和Si100 (c) 4×2二分体之间观察到区域选择性循环添加反应,形成二位数键.
- 计算显示,具有类似碳酸的特征的前体物种决定了观察到的区域选择性.
结论:
- 马尔科夫尼科夫的规则适用于对不对称的基因与不对称的二次体在Si{100}c{4}x2上的循环加法.
- 这些发现为的表面相互作用和反应机制提供了基本的见解.
相关概念视频
[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.
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
Regioselectivity of Electrophilic Additions-Peroxide Effect
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
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.
Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene
The electrophilic addition of hydrogen halides such as HBr to alkenes and nonconjugated dienes gives a single product as per Markovnikov’s rule.


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