Anomeric configuration-dependence of the Lattrell-Dax epimerization from D-glucose to synthetically useful D-allose derivatives  

作　　者：NING Yun-Zhan QIN Chun-Jun SUN Wen-Bin FU Jun-Jie HU Jing YIN Jian 

机构地区：[1]Key Laboratory of Carbohydrate Chemistry and Biotechnology,Ministry of Education,School of Biotechnology,Jiangnan University,Wuxi 214122,China [2]Wuxi School of Medicine,Jiangnan University,Wuxi 214122,China

出　　处：《Chinese Journal of Natural Medicines》2020年第10期723-728,共6页中国天然药物（英文版）

基　　金：the National Natural Science Foundation of China(Nos.21877052 and 21907039);the Natural Science Foundation of Jiangsu Province(Nos.BK20180030and BK20190575);the National First-class Discipline Program of Light Industry Technology and Engineering(No.LITE2018-14);the 111 Project(No.111-2-06)。

摘　　要：D-Allose and its derivatives play important roles in the field of health care and food nutrition. Pure and well-defined Dallose derivatives can facilitate the elucidation of their structure-activity relationship as an essential step for drug design. The LattrellDax epimerization, refers to the triflate inversion using nitrite reagent, is known as valuable method for the synthesis of rare D-allose derivatives. Here, the influence of protecting group patterns on the transformation efficiency of D-glucose derivatives into synthetically useful D-alloses and D-allosamines via the Lattrell-Dax epimerization was studied. For C3 epimerization of D-glucose derivatives bearing O2-acyl group, an anomeric configuration-dependent acyl migration from O2 to O3 was found. In addition, a neighbouring group participation effect-mediated SN1 nucleophilic substitution of the D-glucosamine bearing C2 trichloroacetamido(TCA) group in the Lattrell-Dax epimerization was dependent upon anomeric configuration. Thus, the effect of anomeric configuration on the LattrellDax epimerization of D-glucose suggests that β-D-glucosides with low steric hindrance at C2 should be better substrates for the synthesis of D-allose derivatives. Significantly, the efficient synthesis of the orthogonally protected D-allose 13 and D-allosamine 18 will serve well for further assembly of complex glycans.

关 键 词：D-ALLOSE D-allosamine EPIMERIZATION Anomeric configuration Acyl migration 

分 类 号：R915[医药卫生—微生物与生化药学]