双二碳酸盐作为碳基替代物用于不对称合成. 第二部分. 适用范围和应用
Journal of the American Chemical Society
|July 18, 2001
概括
一种新的非对称基化方法使得从基石二碳酸盐中合成基的酶选择性合成成为可能. 这种催化反应提供了高产量和立体选择性,创造了有价值的性构建块.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 不对称的合成方法
背景情况:
- 基 Ester 是重要的合成中间体.
- 开发对它们的合成进行enantioselective的方法对于获取奇拉分子至关重要.
研究的目的:
- 开发一种新型的,对基乙烯的enantioselective合成.
- 探索基宝石二碳酸盐作为在不对称催化中的前体的实用性.
主要方法:
- 不对称的基石二碳酸盐的基化,使用类的(0) 催化剂与性配体 (R,R-1,2-di(2'-diphenylphosphinobenzamido) cyclohexene).
- 反应优化,包括缓慢的添加程序,以减少反应性核友的反应.
- 由此产生的基的后续合成转化.
主要成果:
- 有效合成有良好的收益率的基.
- 高的区域和酶选择性,通过质核友来实现.
- 适度的enantioselectivities改善了缓慢添加的较少反应的核友.
- 通过异构化,基化和克莱森重组,证明了性向新键的转移.
结论:
- 开发的方法提供了一条有效的途径,以致于获得基丰富的基.
- 基石二碳酸盐作为立体特异双基转换的多功能合成子.
- 该方法允许可预测的性转移,创建复杂的性分子.
相关概念视频
Brønsted-Lowry Acids and Bases
In 1923, the Brønsted–Lowry definition of acids and bases was proposed by Johannes Brønsted and Thomas Lowry. According to this theory, a Brønsted acid is defined as a species that donates a proton in a chemical reaction and gets converted to its conjugate base. A Brønsted base is defined as a species that accepts a proton in a chemical reaction and gets converted into its conjugate acid. These transfers of protons are caused by the displacement of electrons in these reactions, which is...
Leveling Effect and Non-Aqueous Acid-Base Solutions
This lesson defines the leveling effect in acidic and basic solutions and its role in aqueous and non-aqueous solutions. It is essential to understand the competing nature of various species in a chemical system.
The Leveling Effect of a Solvent
A generic acid (HA) reacts with the generic base (B-) to yield the corresponding conjugate base (A-) and conjugate acid (HB):
The Leveling Effect of a Solvent
A generic acid (HA) reacts with the generic base (B-) to yield the corresponding conjugate base (A-) and conjugate acid (HB):
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:
Structures of Carboxylic Acid Derivatives
Structure of Carboxylic Acid Derivatives
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
Carboxylic acid derivatives contain an acyl group attached to a heteroatom such as chlorine, oxygen, or nitrogen. The carbonyl carbon and oxygen are both sp2-hybridized with an unhybridized p orbital.
The three sp2 orbitals of the carbonyl carbon form three σ bonds, one each with the carbonyl oxygen, the α carbon, and the heteroatom, whereas the other two sp2 orbitals of the carbonyl oxygen are occupied by the lone pairs. Further, the unhybridized p...
Acid Halides to Carboxylic Acids: Hydrolysis
Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic acid...
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic acid...
Titration of Polyprotic Base with a Strong Acid
The titration of a polyprotic base such as sodium carbonate with a strong acid such as hydrochloric acid results in two equivalence points on the titration curve. At the first equivalence point, the carbonate ions in the base are completely converted to bicarbonate ions. The second equivalence point corresponds to the complete conversion of bicarbonate ions to carbonic acid, which dissociates into carbon dioxide and water. The region before the first equivalence point corresponds to the...


