One-step selective dehydrogenation of cyclic hemiacetal sugars toward to their chiral lactones  

作　　者：Yulu Zhan Yingshuang Hui Shuqi Wang Lou Gao Yangbin Shen Zhen-Hua Li Yahong Zhang Yi Tang 

机构地区：[1]Department of Chemistry,Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,Laboratory of Advanced Materials,Collaborative Innovation Centre of Chemistry for Energy Materials,Fudan University,Shanghai 200433,China [2]Institute of Materials Science and Devices,Suzhou University of Science and Technology,Suzhou 215009,China

出　　处：《Chinese Chemical Letters》2023年第4期290-295,共6页中国化学快报（英文版）

基　　金：supported by the National Major Research and Development Plan (No. 2018YFA0209402);the National Natural Science Foundation of China (Nos. 21673045, 22088101)。

摘　　要：Chiral glycosyl lactone is an important class of bioactive compound and pharmaceutical intermediate in nature, especially for chiral lactones with 4 carbon atoms, which are very useful building blocks for synthesis of biologically interesting compounds. Herein, a selective dehydrogenation and solvent matched catalytic system under oxygen-free conditions was developed to try to achieve the one-step direct conversion of cyclic hemiacetal sugars toward their chiral glycosyl lactones. During the process, the inherent structural characteristics of sugar was efficiently utilized, and the transfer of its chiral centers was realized. Under the optimum condition, the corresponding lactones were successfully prepared from C_(4)-C6sugars with cyclic hemiacetal structure in acetonitrile. The reaction mechanism in acetonitrile was explored by the first principle density functional theory calculations and tracking reaction process. It was found that the high lactone yield in acetonitrile was due to the high proportion of α-conformation form among multiple tautomers in it. This selective dehydrogenation process may further extend the possibility of the preparation of chiral synthons from carbohydrates directly.

关 键 词：Biomass Cyclic hemiacetal sugars DEHYDROGENATION Chiral lactones CONFORMATION 

分 类 号：O624.5[理学—有机化学]