S-ニトロソチオールの予期せぬバイス結合
Jiming Zhang1, Hua Wang, Ming Xian
1Department of Chemistry, Washington State University, Pullman, Washington 99164, USA.
Journal of the American Chemical Society
|March 5, 2009
まとめ
新しい二結合反応により,不安定なS-ニトロソチオールは,安定した二硫化物-イミノフォスフォラン製品に変換されます. この方法は,温和な条件下での高収量と,タンパク質S-ニトロゼーションの検出における潜在的な応用を提供します.
科学分野:
- 有機化学 オーガニック・ケミストリー
- バイオケミストリー バイオケミストリー
背景:
- S-ニトロソチオールは重要なシグナル伝達分子ですが,化学的に不安定です.
- 生物系におけるS-ニトロゼーションの検出は依然として困難です.
研究 の 目的:
- S-ニトロソチオールを変換するための新しい合成方法を開発する.
- 不安定なS-ニトロソチオールから安定した製品を作る.
- タンパク質S-ニトロゼーションの検出における応用を探求する.
主な方法:
- トリアリル置換のフォスフィン-チオエステル基板を用いた二結合反応.
- 軽度の反応条件が採用されました.
主要な成果:
- 安定した二硫化物-イミノフォスフォラン製品の高収量を達成しました.
- この反応は,原発S-ニトロソチオールを効果的に変換した.
結論:
- S-ニトロソチオール変換のための新しい効率的な方法が確立されています.
- 開発された反応は,タンパク質システムにおけるS-ニトロゼーションの検出に希望を示しています.
関連する概念動画
Preparation and Reactions of Thiols
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.
2° Amines to N-Nitrosamines: Reaction with NaNO2
Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
Preparation and Reactions of Sulfides
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.
Structure and Nomenclature of Thiols and Sulfides
Thiols and sulfides are sulfur analogs of alcohols and ethers, respectively, where the sulfur atom takes the place of the oxygen atom. Thus, thiols are generally represented as RSH, where R is an alkyl substituent and —SH is the functional group. On the other hand, in sulfides, the central sulfur atom is bonded to two hydrocarbon groups on either side. Depending upon the type of group, sulfides can be either symmetrical or asymmetrical. Both thiols and sulfides display a bent geometry, similar...
Nitrosation of Enols
The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.
Electrophilic Aromatic Substitution: Nitration of Benzene
The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.


