Exploring the Far Side of Glycosyl Sulfoxide Activation Process
Exploring the Far Side of Glycosyl Sulfoxide Activation Process
复制标题
探索糖基亚砜活化过程的另一面
DOI：
10.1002/cjoc.202200706
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发表时间：
2022-11
影响因子：
5.4
通讯作者：
Qian Wan
中科院分区：
文献类型：
--
作者：
Wei Chen;Pinru Wu;Jing Zeng;Zhiwen Liao;Lei Cai;Hao Wang;Lingkui Meng;Qian Wan
卡恩糖基化的发现使碳水化合物化学向前迈进了一大步。尽管进行了一系列广泛的研究，但这种强大的糖基化的确切机制仍未完全了解。为了解决这些30年的难题，本研究探索了Kahne糖基化的远端。经过一系列的控制和跟踪实验，提出了一些重要的中间体，包括糖基氧磺胺离子和亚酸酐（Crich's中间体），可能是复杂反应途径的原因。研究还表明，除了传统的离子糖基化途径外，一种新的自由基途径很可能产生各种副产物和副产物。本研究为进一步了解Kahne糖基化提供了依据，也为如何提高亚砜基糖基化反应的效率提供了思路。
Comprehensive SummaryThe discovery of Kahne glycosylation forwards a big step in the carbohydrate chemistry. Despite an extensive series of studies, the precise mechanism of this powerful glycosylation is still not fully understood. To address these 30‐year puzzles, the far side of Kahne glycosylation is explored in this study. After a series of control and tracking experiments, a number of important intermediates including glycosyl oxo‐sulfonium ion and sulfenic anhydride (Crich's intermediate) are suggested to be responsible for the complex reaction pathway. It also reveals that in addition to the conventional ionic glycosylation pathway, a novel free radical pathway is very likely to contribute to the various side‐and co‐products. This study provides further understanding of Kahne glycosylation, and it also sheds light on how to improve the efficiency of sulfoxide‐based glycosylation reactions.