氨基酸催化合艾伦酸以α,β不和碳酸
Catherine A Evans1, Scott J Miller
1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467-3860, USA.
Journal of the American Chemical Society
|October 9, 2003
概括
核氨酸使得1,4-添加的艾伦基向不和碳烯化合物. 这种反应允许在温和条件下进行复杂分子的单三元合成.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
背景情况:
- 阿尔法,β不和碳烯化合物是多功能合成中间体.
- 艾伦酸乙是有机合成中有价值的构建块.
- 开发有效的催化方法来形成碳-碳键是至关重要的.
研究的目的:
- 为了研究核胺在1,4-添加的艾伦基的催化活性.
- 探索贝利斯-希尔曼产品在这种反应中作为电友的使用.
- 开发一个一子,三组件合策略.
主要方法:
- 使用各种核胺的催化反应选.
- 反应条件 (温度,溶剂,度) 的优化.
- 对基质范围和功能组耐受性的研究.
主要成果:
- 核胺有效催化了1,4-添加的艾伦酸以α,β不和碳烯化合物.
- 在温和的条件下,反应有效地进行.
- 贝利斯-希尔曼导引物被成功地用作电友,使一个一个,三组件合.
结论:
- 核胺催化提供了一条有效的途径,用于合添加艾伦基.
- 开发的单三组分反应为合成复杂分子提供了一种简化方法.
- 这种方法扩大了艾伦和贝利斯-希尔曼产品的合成效用.
相关概念视频
Aldehydes and Ketones with Alcohols: Hemiacetal Formation
Similar to water, alcohols can add to the carbonyl carbon of the aldehydes and ketones. The addition of one molecule of alcohol to the carbonyl compound forms the hemiacetal or half acetal. As depicted below, in a hemiacetal, the carbon is directly linked to an OH and OR group.
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
Amines to Alkenes: Hofmann Elimination
Alkenes can be obtained from amines via an E2 elimination. The amine is first converted into a good leaving group, such as a quaternary ammonium salt. This is accomplished by treating the amine with an excess of alkyl halide, which results in a halide salt. Next, the halide salt is transformed into a hydroxide salt that functions as a base to enable elimination.
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
Acid-Catalyzed Aldol Addition Reaction
The aldol reaction of a ketone under acidic conditions successfully forms an unsaturated carbonyl as the final product instead of an aldol. The acid-catalyzed aldol reaction is depicted in Figure 1.
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.


