催化非对称的N-托西尔胺基因的阿里化
Ryo Shintani1, Momotaro Takeda, Takaoki Tsuji
1Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan. shintani@kuchem.kyoto-u.ac.jp
Journal of the American Chemical Society
|September 3, 2010
概括
研究人员开发了一种催化反应,用于制造性氨基衍生物. 这种方法使用不对称的催化剂有效地产生具有挑战性α-四替代碳立体中心的化合物.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 立体化学是一种立体化学.
背景情况:
- N-托西尔胺是有机合成中的多功能前体.
- 构建α-四替代碳立体中心仍然是合成化学的一个重大挑战.
- 不对称的催化对于获取质纯化合物至关重要.
研究的目的:
- 开发一种新的催化方法,用于合成性氨基衍生物.
- 为了实现α-tetrasubstituted碳立体中心的高度enantioselective构造.
- 探索四基酸盐在不对称催化剂中的实用性.
主要方法:
- 催化添加反应. 催化添加反应.
- 使用四基酸盐作为核友.
- 为了不对称的诱导,采用了一种性二烯联体.
主要成果:
- 成功合成了性氨基衍生物.
- 在α-四替代碳立体中心的形成中实现了高的反反选择性.
- 证明了催化不对称添加的效率.
结论:
- 开发的催化方法提供了一条有效的途径,以获得有价值的性氨基衍生物.
- 使用奇拉二烯配体是实现高反选择性的关键.
- 这种方法扩大了复杂分子不对称合成的工具包.
更多相关视频
相关概念视频
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo, or cyano...
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo, or cyano...
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
Nitriles to Ketones: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert nitriles to ketones and proceed through a nucleophilic acyl substitution. Nitriles react with a Grignard reagent, followed by an aqueous acid, to yield ketones. The reaction introduces a new carbon–carbon bond. The alkyl–magnesium bond in the Grignard reagent is highly polar, so the alkyl carbon develops a carbanionic character and acts as a nucleophile.
The mechanism begins with a nucleophilic attack by the Grignard reagent...
The mechanism begins with a nucleophilic attack by the Grignard reagent...
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
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...
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...


