(Eta2-alkyne) methyl(dioxo) 复合物作为化olefination的催化剂
Ana M Santos1, Carlos C Romão, Fritz E Kühn
1Instituto de Tecnologia Química e Biológica da Universidade Nova de Lisboa, Quinta do Marquês, EAN, Apt 127, 2781-901 Oeiras, Portugal.
Journal of the American Chemical Society
|February 27, 2003
概括
甲基二氧化复合物催化阿尔德海德化反应. 谱学研究揭示了一种涉及素形成和活性碳基物种生成的机制,以实现高效的催化.
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:
- 甲基二氧化复合物是已知的催化剂.
- 化反应在有机合成中至关重要.
- 了解催化机制是开发新反应的关键.
研究的目的:
- 为了研究CH3ReO2L复合物的催化机制在化olefination.
- 为了确定参与催化循环的活性物种.
- 为了阐明酸中间体的作用.
主要方法:
- 合成和表征CH3ReO2L复合物 (L=2-丁,3-,二乙烯).
- 使用4-甲 (4-nba) 和乙烯酸乙 (eda) 的olefination反应.
- 现场光谱研究包括31P,17O,13C和1H NMR.
主要成果:
- CH3ReO2L复合物有效地催化化的化.
- 光谱学数据表明,作为最初的步骤,快速形成素.
- 活性碳基物种是通过酸与二氧化金属复合物的反应而形成的.
结论:
- 油脂化机制涉及酸中间体.
- 活跃的催化物是一种金属碳酸.
- 这项研究提供了有关甲基二氧化物复合物的催化循环的见解.
相关概念视频
E2 Reaction: Kinetics and Mechanism
SN2 substitutions and E2 eliminations of alkyl halides proceed via a concerted pathway. While the nucleophile attacks the alpha carbon in SN2 reactions, it functions as a strong base and abstracts a beta hydrogen in the E2 mechanism. The rate-limiting transition state in E2 elimination reactions is characterized by partially broken carbon–hydrogen and carbon–halogen bonds and a partially formed pi bond between the alpha and beta carbons. The beta hydrogen and halide are eliminated...
E2 Reaction: Stereochemistry and Regiochemistry
Elimination reactions of alkyl halides can yield one or more alkenes depending on the specific regiochemical and stereochemical considerations. While the regiochemistry of the reaction governs the location of the double bond in the product, the stereochemical requirements often influence the geometry.
When a substrate with two different β hydrogens undergoes an E2 elimination, the presence of a strong base can yield two regioisomeric alkenes. The more-substituted alkene is the major product and...
When a substrate with two different β hydrogens undergoes an E2 elimination, the presence of a strong base can yield two regioisomeric alkenes. The more-substituted alkene is the major product and...
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
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.
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.
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.


