一个意想不到的S-尼特罗斯醇的双结合
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
概括
一种新的双联结反应将不稳定的S-二醇转化为稳定的二硫化物-氨基酸产物. 这种方法在温和条件下提供了高产量和在检测蛋白质S-化中的潜在应用.
科学领域:
- 有机化学 有机化学
- 生物化学 生物化学
背景情况:
- 酸醇是关键的信号分子,但在化学上不稳定.
- 在生物系统中检测S-化仍然具有挑战性.
研究的目的:
- 开发一种新的合成方法来转化S-nitrosothiols.
- 从不稳定的S-nitrosothiols中制造稳定的产品.
- 探索检测蛋白质S-化中的应用.
主要方法:
- 一种使用酸替代酸基质的双结合反应.
- 使用了轻度反应条件.
主要成果:
- 实现了稳定的二硫化物 - 胺基酸产品的高产量.
- 这种反应有效地转化了原始的S-尼特罗斯醇.
结论:
- 已经建立了一种新的,高效的S-nitrosothiol转化方法.
- 开发的反应显示了蛋白质系统中S-化检测的前景.
相关概念视频
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.


