Anomeric configuration-dependence of the Lattrell-Dax epimerization from D-glucose to synthetically useful D-allose derivatives.
10.1016/S1875-5364(20)60012-7
- Author:
Yun-Zhan NING
1
;
Chun-Jun QIN
1
;
Wen-Bin SUN
1
;
Jun-Jie FU
1
;
Jing HU
2
,
3
;
Jian YIN
4
Author Information
1. Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, School of Biotechnology, Jiangnan University, Wuxi 214122, China.
2. Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, School of Biotechnology, Jiangnan University, Wuxi 214122, China
3. Wuxi School of Medicine, Jiangnan University, Wuxi 214122, China.
4. Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, School of Biotechnology, Jiangnan University, Wuxi 214122, China. Electronic address: jianyin@jiangnan.edu.cn.
- Publication Type:Journal Article
- Keywords:
Acyl migration;
Anomeric configuration;
D-allosamine;
D-allose;
Epimerization
- From:
Chinese Journal of Natural Medicines (English Ed.)
2020;18(10):723-728
- CountryChina
- Language:English
-
Abstract:
D-Allose and its derivatives play important roles in the field of health care and food nutrition. Pure and well-defined D-allose derivatives can facilitate the elucidation of their structure-activity relationship as an essential step for drug design. The Lattrell-Dax 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 S1 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 Lattrell-Dax 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.
