基的动态动态不对称化和化
Lin-Xin Ruan1, Bo Sun1, Jia-Ming Liu1
1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China.
概括
这项研究引入了一种新的催化方法,用于制造富含的三级酒精. 该过程有效地从简单的和有机酸盐中产生具有两个相邻立体中心的分子.
科学领域:
- 有机化学
- 催化剂
- 医学化学
背景情况:
- 缩醇是制药和材料科学的重要组成部分.
- 用两个连续的立体中心合成三级醇是一个重要的合成挑战.
- 现有的方法往往缺乏对这些复杂结构的效率和选择性.
研究的目的:
- 开发一种高效和高度选择性的方法,用于构建两个相连的立体中心的缩三级酒精.
- 建立适用于药物化学和总合成的多功能平台.
主要方法:
- 使用催化不对称的器官酸盐添加到非激活酸盐中.
- 采用动态动态不对称的加法策略,涉及基和基核友.
- 开发了一种无基化工艺.
主要成果:
- 在单个步骤中制备各种α,β-基拉三级酒精.
- 在产品中表现出高水平的二重选择性和反选择性.
- 已成功应用该方案来修改药物和合成生物相关的分子.
结论:
- 报告的催化方法为合成复杂的醇提供了强大且广泛适用的策略.
- 动态运动不对称的加法提供了一种新的方法来克服立体选择合成的挑战.
- 这种无基化过程预计将成为未来动态运动过程的宝贵工具.
相关概念视频
α-Alkylation of Ketones via Enolate Ions
3.2K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
3.2K
Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes
3.9K
Aldehydes and ketones are prepared from alcohols, alkenes, and alkynes via different reaction pathways. Alcohols are the most commonly used substrates for synthesizing aldehydes and ketones. The conversion of alcohol to aldehyde, which involves the oxidation process, depends on the class of the alcohol used and the strength of the oxidizing agent. For instance, primary alcohol will form an aldehyde when treated with a weak oxidizing agent; however, it gets over-oxidized to a carboxylic acid in...
3.9K
Factors Affecting α-Alkylation of Ketones: Choice of Base
3.3K
α-Alkylation of ketones is achieved in the presence of alkyl halides and a base. The reaction proceeds via the formation of an enolate ion followed by nucleophilic substitution. The choice of base employed is essential as it is the key factor in determining the reaction outcome.
The reaction involving bases like EtO− whose conjugate acid EtOH (pKa = 15.9) is stronger than the ketone (pKa = 19.2) results in an equilibrium mixture with higher ketone concentration. As a consequence,...
The reaction involving bases like EtO− whose conjugate acid EtOH (pKa = 15.9) is stronger than the ketone (pKa = 19.2) results in an equilibrium mixture with higher ketone concentration. As a consequence,...
3.3K
Acid-Catalyzed α-Halogenation of Aldehydes and Ketones
4.0K
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...
4.0K
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
18.6K
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
18.6K
Aldol Condensation with β-Diesters: Knoevenagel Condensation
3.1K
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.
3.1K


