最少保护糖的选择性,立体控制的糖化
Qiuhan Li1, Samuel M Levi1, Corin C Wagen1
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, USA.
Nature
|June 16, 2022
概括
化学家开发了小分子催化剂,用于选择性糖化未受保护的糖. 这一突破提供了复杂碳水化合物的高效合成,
科学领域:
- 合成化学
- 碳水化合物化学
- 有机合成
背景情况:
- 氧糖化合物合成具有挑战性,需要精确控制糖化反应.
- 传统的方法依赖于多步保护组策略,这些策略往往是低效的.
- 在未受保护的糖类中实现位点和立体选择性仍然是一个重大障碍.
研究的目的:
- 开发一种对未受保护碳水化合物的选择性糖化方法.
- 允许在没有广泛的保护组的情况下进行位点和立体选择性糖键的形成.
- 探索小分子催化剂用于碳水化合物功能化.
主要方法:
- 新型 bis-thiourea 小分子催化剂的设计和合成.
- 用于未受保护的单糖和分糖的立体和位点选择性糖化催化剂.
- 动态和计算研究以阐明选择性的机制.
主要成果:
- 实现了高度立体和位点选择性的银河系和人体系.
- 使用未受保护或最小保护的糖,证明了各种多功能核的成功糖化.
- 确定了催化剂和核之间的稳定C-H/π相互作用是选择性的关键.
结论:
- 小分子催化剂可以有效控制糖化反应中的立体和位点选择性.
- 稳定非共价相互作用在实现选择性方面起着至关重要的作用,模仿生物系统.
- 这种方法为选择性碳水化合物功能化提供了通用和有效的策略,绕过了传统的保护组方法.
相关概念视频
Oligosaccharide Assembly
3.0K
Protein glycosylation starts in the ER lumen and continues in the Golgi apparatus. Glycosyltransferases catalyze the addition of sugar molecules or glycosylation of proteins. Usually, these enzymes add sugars to the hydroxyl groups of selected serine or threonine residues to form O-linked glycans or the amino groups of asparagine residues to form N-linked glycans. Different positions on the same polypeptide chain can contain differently linked glycans.
Multiple sugar molecules that may or may...
Multiple sugar molecules that may or may...
3.0K
Protein Glycosylation
7.2K
Glycosylation, the most common post-translational modification for proteins, serves diverse functions. Adding sugars to proteins makes the proteins more resistant to proteolytic digestion. Glycosylated proteins can act as markers and receptors to promote cell-cell adhesion. Additionally, they have many essential quality control functions in the cell, such as correct protein folding and facilitating transport of misfolded proteins to the cytosol, which can be degraded.
Glycosylation occurs in...
Glycosylation occurs in...
7.2K
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 Acid-Catalyzed Hydration
8.6K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
8.6K
Biosynthesis of Polysaccharides
81
Polysaccharides such as glycogen and starch are synthesized from nucleoside diphosphate sugars, primarily uridine diphosphate glucose (UDPG) and adenosine diphosphate glucose (ADPG). These activated glucose donors act as key intermediates in carbohydrate metabolism and biosynthesis. UDPG primarily involves glycogen synthesis in animals and many bacteria, while ADPG plays a fundamental role in starch synthesis in plants and certain bacteria.UDPG is formed when glucose-1-phosphate reacts with...
81
SN1 Reaction: Stereochemistry
8.8K
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...
8.8K


