通过E选择性olefination的以诺酸盐与的合成四位置换和功能化的乙烯
Mitsuru Shindo1, Taisuke Kita, Toshihiro Kumagai
1Institute of Health Biosciences, The University of Tokushima Graduate School, Japan. shindo@cm.kyushu-u.ac.jp
Journal of the American Chemical Society
|January 26, 2006
概括
研究人员创建了一种新方法,用于碳基的E选择性油脂化,产生功能化油脂. 他们还成功地将C-S插入到醇 Ester中,使用ynolates生产β-基醇 Ester.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 化反应对于合成复杂的有机分子至关重要.
- 开发用于产生高度替代的烯酸的选择性方法仍然是一个挑战.
研究的目的:
- 开发一种新的碳烯 Ester 的 E-选择性油脂细化方法.
- 为了实现C-S插入到乙基乙醇以合成β-基托乙基乙醇.
主要方法:
- 使用伊诺酸盐作为关键中间体.
- 开发了E选择性油脂精制的特定反应条件.
- 研究了C-S插入反应机制.
主要成果:
- 成功合成了具有高E选择性的四位置换,功能化的烯酸.
- 通过C-S插入醇产生的β-基托醇.
- 证明了因诺酸盐中间体的多功能性.
结论:
- 开发的方法提供了一条有效的途径,以获得有价值的烯酸化合物.
- 这项工作扩大了因诺酸盐在有机合成中的合成效用.
相关概念视频
Preparation of Epoxides
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Carboxylic Acid Derivatives: Overview
Carboxylic acid derivatives are formed by replacing the hydroxyl group of carboxylic acids with a different functional group. The most common carboxylic acid derivatives are:
Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
Hydrolysis of esters under acidic conditions proceeds through a nucleophilic acyl substitution. In the presence of excess water, the reaction proceeds in a reversible manner, forming carboxylic acids and alcohols.
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
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.
Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an alkylated β-keto acid.
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.


