Enantiodivergent Relay Couplingによるラセミックサイクロプロピルジンク反応物のステレオ選択的機能化
Lun An1, Fei-Fei Tong1, Shu Zhang2
1Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Journal of the American Chemical Society
|June 13, 2020
まとめ
この研究は,ラセミックサイクロプロピルシンク反応剤からキラルサイクロプロパンを合成するためのエナチダイバーゲント戦略を導入する. この方法は,薬用化学の用途のために,対極の構成を持つ有価なキラル・サイクロプロパンを効率的に生成します.
科学分野:
- 有機化学
- 非対称合成
背景:
- 移行金属触媒はキラル分子を作るための鍵です.
- ステレオ選択的中間生成の難しさのために,ラセミック前駆体からキラルサイクロプロパンを合成することは困難です.
研究 の 目的:
- 多種多様なキラル・サイクロプロパンを合成するための効率的なエナチダイバーゲント戦略を開発する.
- エナティオメリックに濃縮されたサイクロプロパンを作るためのラセミックサイクロプロピルシンク反応剤を使用する.
主な方法:
- 一つのポット,二段階の enantiodivergent リレーカップリングプロセス.
- ラセミックシス・サイクロピルジンク反応剤のニッケル触媒運動解像度
- ステレオスペシフィック・リレー・カップリングで,様々な電ophilesがある.
主要な成果:
- フロオアルキル化およびキラル側鎖の変種を含む機能化されたキラルサイクロプロパンの効率的な合成.
- 異なった構成のキラル・サイクロプロパン2種を,単一のラセミク・出発材料から製造する.
- シントロンとしてのキラル・サイクロプロパンの汎用性の実証.
結論:
- enantiodivergentリレーカップリング戦略は,多様なキラルサイクロプロパンにアクセスできます.
- この方法は,ラセミック二次アルキル金属核性物質の使用の制限を克服します.
- 合成されたキラル・サイクロプロパンは,潜在的に薬用である構造的に多様な分子を作るのに価値があります.
![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
関連する概念動画
02:05Prochirality
4.7K
The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...
4.7K
02:17Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
16.0K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
16.0K
01:12Stereochemical Effects of Enolization
2.5K
The chiral α-carbon of the carbonyl compound is the stereocenter of the molecule. As shown in the figure below, when such a carbonyl compound undergoes racemization under an acidic or basic condition, an achiral enol is formed.
2.5K
02:15SN1 Reaction: Stereochemistry
10.0K
This lesson provides an in-depth discussion of the stereochemical outcomes in an SN1 reaction.
In the first step of an SN1 reaction, the bond between the electrophilic carbon and the leaving group ionizes to generate the carbocation intermediate. The second step of the mechanism is the nucleophilic attack.
In the formed carbocation, the positively charged carbon is sp2 hybridized with a trigonal planar geometry. As all the three substituents lie on the same plane, a plane of symmetry for the...
In the first step of an SN1 reaction, the bond between the electrophilic carbon and the leaving group ionizes to generate the carbocation intermediate. The second step of the mechanism is the nucleophilic attack.
In the formed carbocation, the positively charged carbon is sp2 hybridized with a trigonal planar geometry. As all the three substituents lie on the same plane, a plane of symmetry for the...
10.0K
02:35Regioselectivity of Electrophilic Additions-Peroxide Effect
10.0K
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
10.0K
01:29Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
5.3K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
5.3K