硫黄原子のイソチオウレア触媒による共振活性化による硫黄ミドール誘導体の非対称合成のためのS(VI) ステレオジェニシティの制御
Benpeng Li1,2, Junyuan Hu3, Zhengtao Xu1
1State Key Laboratory of Green Pesticide; Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Center for R&D of Fine Chemicals of Guizhou University, Huaxi District, Guiyang, 550025, China.
Angewandte Chemie (International ed. in English)
|August 30, 2025
まとめ
この研究では,キラル硫黄 (VI) 化合物を生成するための新しい有機触媒法が導入されています. このアプローチは,硫黄胺酸のエナンチオセレクティブ合成を可能にし,重要なキラル硫黄基板へのアクセスを拡大します.
科学分野:
- 有機化学
- アシンメトリック・シンセシス
- 器官触媒
背景:
- キラル硫黄 (IV) 化合物の製造には大きな進展がみられた.
- キラル硫黄のステレオ制御を達成することは,合成化学における重要な課題です.
研究 の 目的:
- S ((VI) -キラル硫黄酸塩のエナンチオセレクティブ合成のための新しい有機触媒法を開発する.
- S ((VI) ステレオジェニシティをターゲットとしたイソチオウレア有機触媒の新しい活性化モードを確立する.
主な方法:
- イソチオウレア触媒を用いたラセミックS ((VI) スルフォニミドイル塩化物の共性活性化.
- キラルイソチオウレア結合のスルフォニミドイル中間物質の形成
- ダイナミック・キネティック・アシンメトリック・トランスフォーメーション (DYKAT) による非対称S−O結合形成.
主要な成果:
- 高い収量を持つS ((VI) -キラル硫黄酸塩の高度なエナンチオセレクティブ合成.
- C原子活性化とは異なる新しいS原子活性化戦略の実証.
- DYKATにおけるステレオジェニック・センター・インバーションの重要性を明らかにする機械的洞察.
結論:
- 開発された方法は,エナチオ濃縮されたS ((VI) -キラルスルフォニミダートへの効率的なアクセスを提供します.
- これらの中間物質は,様々なS (VI) -ステロゲンフレームワークの迅速な合成を促進します.
- 合成された化合物は,植物病原体に対する抗菌作用を示す.
関連する概念動画
Preparation and Reactions of Sulfides
5.1K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
5.1K
Preparation and Reactions of Thiols
6.7K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
6.7K
SN2 Reaction: Stereochemistry
9.8K
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
9.8K
Regioselectivity and Stereochemistry of Hydroboration
8.4K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.4K
Electrophilic Aromatic Substitution: Sulfonation of Benzene
6.4K
Sulfonation of benzene is a reaction wherein benzene is treated with fuming sulfuric acid at room temperature to produce benzenesulfonic acid. Fuming sulfuric acid is a mixture of sulfur trioxide and concentrated sulfuric acid.
6.4K
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
2.0K
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...
2.0K

![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)
