化学
衍生化
组合化学
表面改性
单糖
共价键
催化作用
分子
背景(考古学)
分子识别
选择性
功能群
基质(水族馆)
小分子
有机化学
聚合物
生物化学
物理化学
古生物学
地质学
高效液相色谱法
海洋学
生物
作者
Xiaopeng Sun,Hyelee Lee,Sunggi Lee,Kian L. Tan
出处
期刊:Nature Chemistry
[Springer Nature]
日期:2013-08-11
卷期号:5 (9): 790-795
被引量:127
摘要
Carbohydrates and natural products serve essential roles in nature, and also provide core scaffolds for pharmaceutical agents and vaccines. However, the inherent complexity of these molecules imposes significant synthetic hurdles for their selective functionalization and derivatization. Nature has, in part, addressed these issues by employing enzymes that are able to orient and activate substrates within a chiral pocket, which increases dramatically both the rate and selectivity of organic transformations. In this article we show that similar proximity effects can be utilized in the context of synthetic catalysts to achieve general and predictable site-selective functionalization of complex molecules. Unlike enzymes, our catalysts apply a single reversible covalent bond to recognize and bind to specific functional group displays within substrates. By combining this unique binding selectivity and asymmetric catalysis, we are able to modify the less reactive axial positions within monosaccharides and natural products. The manipulation of complex molecules offers an avenue for developing new therapeutics and biological probes. Here, a catalyst is described that forms a covalent bond to the substrate before selectively functionalizing a proximal functional group. Cis-1,2-diols are targeted allowing for the derivatization of the axial hydroxyls of monosaccharides in the presence of unprotected equatorial hydroxyls.
科研通智能强力驱动
Strongly Powered by AbleSci AI