Exploring the Far Side of Glycosyl Sulfoxide Activation Process  

作　　者：Wei Chen Pinru Wu Jing Zeng Jing Fang Zhiwen Liao Lei Cai Hao Wang Lingkui Meng Qian Wan 

机构地区：[1]Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation,School of Pharmacy,Huazhong University of Science and Technology,13 Hangkong Road,Wuhan,Hubei,430030 China [2]Wuhan Union Hospital of China,Huazhong University of Science and Technology,1277 Jiefang Avenue,Wuhan,Hubei,430022 China

出　　处：《Chinese Journal of Chemistry》2023年第4期383-391,共9页中国化学（英文版）

基　　金：The National Natural Science Foundation of China(22025102,22077039,21877043);the Open Projects Fund of Shandong Key Laboratory of Carbohydrate Chemistry and Glycobiology,Shandong University(2021CCG02);the Fundamental Research Funds fortheCentralUniversities,HUST(2019kfyXKJC080,2019JYCXJJ046,2019kfyRCPY034)were appreciated.

摘　　要：The 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.

关 键 词：Carbohydrates Kahne glycosylation RADICALS Reaction mechanisms Reactive intermediates 

分 类 号：O62[理学—有机化学]