催化性,enantioselective,结合性基因的添加
Thomas F Knöpfel1, Pablo Zarotti, Takashi Ichikawa
1Laboratorium für Organische Chemie, ETH Hönggerberg, CH-8093 Zürich, Switzerland.
Journal of the American Chemical Society
|July 7, 2005
概括
这项研究引入了一种使用终端乙烯的新型铜催化酶选择性结合物添加. 反应在水中有效地进行,利用称为PINAP的新P,N-连接体以获得最佳结果.
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:
- 结合加法反应是有机合成的基础.
- 开发直接基因功能化的enantioselective方法仍然是一个挑战.
- 对于可持续化学,水性介质和温和条件是理想的.
研究的目的:
- 开发一种新型的铜催化酶选择性结合添加终端乙烯的新型结合添加剂.
- 为了实现乙烯与Meldrum的酸衍生物的直接功能化.
- 在环境条件下在水性介质中进行反应.
主要方法:
- 使用终端乙 (乙) 的铜催化反应.
- 在现场甲化乙.
- 使用梅尔德鲁姆的酸衍生接受器.
- 采用一种称为PINAP的新一类P,N-连接体.
主要成果:
- 成功添加基乙烯的反选择性结合物.
- 反应在没有惰性大气的水性介质中进行.
- 证明了PINAP连接体在优化方面的实用性.
- 实现了高效率和选择性.
结论:
- 一种新且高效的铜催化酶选择性结合添加终端乙烯已经开发出来.
- 使用PINAP配体对于反应的成功至关重要.
- 该方法为水性介质中的基因功能化提供了一种可持续的方法.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Conjugate Addition to α,β-Unsaturated Carbonyl Compounds
α,β-Unsaturated carbonyl compounds are molecules bearing a carbonyl and alkene functionality in conjugation with each other. The conjugation in the molecule leads to three resonance structures. The hybrid form exhibits two probable electrophilic sites: the carbonyl carbon and the β carbon.
Conjugate Addition of Enolates: Michael Addition
The attack of a nucleophile at the β carbon of an α,β-unsaturated carbonyl compound is called conjugate addition. Conjugate addition reactions of active methylene compounds, such as β-diketones, β-keto esters, β-keto nitriles, and α-nitro ketones, are called Michael addition reactions.
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.
Conjugate Addition (1,4-Addition) vs Direct Addition (1,2-Addition)
α,β-Unsaturated carbonyl compounds with two electrophilic sites, the carbonyl carbon, and the β carbon, are susceptible to nucleophilic attack via two modes: conjugate or 1,4-addition and direct or 1,2-addition.
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are formed faster owing to...
Conjugate addition results in a thermodynamically stable product. The reaction retains the stronger C=O bond at the expense of the weaker C=C π bond. The process is slow as the β carbon is less electrophilic than the carbonyl carbon.
Direct addition products are formed faster owing to...


