Stereoelectronic Control of Cleavage of Dioxolane Five-membered Ring on Carbohydrates  

作　　者：PAN Xiao-liang ZHOU Yi-xuan LIU Wei LIU Jing-yao DONG Hai 

机构地区：[1]State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130021, P. R. China [2]School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, P. R. China

出　　处：《Chemical Research in Chinese Universities》2013年第3期551-555,共5页高等学校化学研究（英文版）

基　　金：Supported by the National Natural Science Foundation of China（No.20973077）, the Program for New Century Excellent Talents in University of China（No.NCET-07-0358） and the Brain Gain Fund of Huazhong University of Science and Technology, China.

摘　　要：A mechanism about the origin of the selectivities for the cleavage of dioxolane five-membered rings on pyranoside rings was suggested. Quantum chemical studies were performed to testify the rationality of the mechanism. It is thus suggested that the selectivities should be dependent on the differences of the free energy at the transition states when the five-membered ring cleaves. Natural bond orbital（NBO） analysis was further made to assess the influence of stereoelectronic effects on the selectivities.A mechanism about the origin of the selectivities for the cleavage of dioxolane five-membered rings on pyranoside rings was suggested. Quantum chemical studies were performed to testify the rationality of the mechanism. It is thus suggested that the selectivities should be dependent on the differences of the free energy at the transition states when the five-membered ring cleaves. Natural bond orbital（NBO） analysis was further made to assess the influence of stereoelectronic effects on the selectivities.

关 键 词：Stereoelectronic effect CARBOHYDRATE Antiperiplanar lone-pair hypothesis 

分 类 号：O621.3[理学—有机化学] TQ23[理学—化学]