Appraisal of an oligomerization behavior of unprotected carbohydrates induced by phosphorus reagent

作者：Yuan, Hang; Yang, Xu; Chen, Peng; Liu, Yan^*; Tang, Guo; Zhao, Yufen^*

来源：Science China Chemistry, 2018, 61(2): 243-250.

DOI：10.1007/s11426-017-9165-4

• organic phosphorus activation
• oligosaccharide
• oligomerization
• one-pot unprotected synthesis

In this article, a novel oligomerization behavior of unprotected monosaccharides was discovered in a one-pot reaction induced by phosphorus reagent at room temperature. The inherent characteristics of the oligomerization reaction were dissected in detail by mass spectrometry based method combined with NMR technology. It was found that the main glycosidic bonding pattern is (1 -> 6) linkage with 66% regioselectivity for each step. The ratio of alpha-(1 -> 6) and beta-(1 -> 6) glycosidic bonds formed is around 1:1. The reactivity of 1-OH group from aldoses and the driving force from penta-coordinated phosphorus intermediates are the two critical factors for the oligomerization, according to the monitoring experiments by ESI-MS and NMR. Besides, the oligomerization reaction has good compatibility for various aldoses and could expand to O-glycosylated modification of peptides in vitro. The above results will provide a novel enlightenment to develop more convenient and higher-efficient methods for the synthesis of oligosaccharide library.

• 出版日期2018-2
• 单位清华大学; 厦门大学