随机选择性有机催化氨基合物添加
Young K Chen1, Masanori Yoshida, David W C MacMillan
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Journal of the American Chemical Society
|July 20, 2006
概括
这项研究引入了第一个enantioselective有机催化氨基合物添加. 这种新的方法高效地通过iminium催化合成有价值的β-氨基甲基化中间体.
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:
- 在有机合成中,开发用于C-N键形成的enantioselective方法至关重要.
- 有机催化剂为复杂分子结构提供一种无金属的替代方案.
研究的目的:
- 开发了第一个enantioselective有机催化氨基合氨基添加反应.
- 为了使有价值的性β-氨基化物中间体的合成.
主要方法:
- 使用LUMO降低的阴催化剂.
- 使用一种合理设计的N-silyloxycarbamate核 (HOMO-raised).
- 选了以imidazolidinone 2*pTSA作为有机催化剂.
主要成果:
- 实现了对α,β不和化物具有高度化学和酶选择性的1,4-添加.
- 成功催化了各种N受保护的西基酸盐的添加.
- 生成的合成有用的β-氨基化物中间体.
结论:
- 开发的协议代表了对抗选择性氨基合物添加的重大进步.
- 通过快速合成富含乙的β-氨基酸和1,3-氨基醇,证明了合成效用.
相关概念视频
Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
Nucleophilic Addition to the Carbonyl Group: General Mechanism
The carbonyl carbon in an aldehyde or ketone is the site of a nucleophilic attack due to its electron-deficient nature. Depending on the strength of the incoming nucleophile, the reaction occurs via different mechanistic pathways.
A stronger nucleophile can directly attack the electrophilic center, the carbonyl carbon. The HOMO orbital of the nucleophile interacts with the LUMO (π* antibonding) orbital present on the carbonyl carbon. This interaction breaks the π bond and shifts the π bonding...
A stronger nucleophile can directly attack the electrophilic center, the carbonyl carbon. The HOMO orbital of the nucleophile interacts with the LUMO (π* antibonding) orbital present on the carbonyl carbon. This interaction breaks the π bond and shifts the π bonding...
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 (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...
Catalysis
Catalysis influences the rate of chemical reactions by providing an alternative reaction pathway with lower activation energy. A catalyst speeds up a reaction, but it is not consumed during the process. The fundamental principle of catalysis is the ability of a catalyst to alter the reaction mechanism, often introducing a more efficient pathway than the uncatalyzed process.In a catalyzed reaction, the catalyst participates directly in the reaction mechanism. It interacts with reactants to form...
Heterogeneous Catalysis
Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...


