1-Picolinyl-5-azido Thiosialosides: Versatile Donors for the Stereoselective Construction of Sialyl Linkages

Jian Chen, Thomas Hansen, Qing Ju Zhang, De Yong Liu, Yao Sun, Hao Yan, Jeroen D.C. Codée, Richard R. Schmidt*, Jian Song Sun

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


With the picolinyl (Pic) group as a C-1 located directing group and N3 as versatile precursor for C5-NH2, a novel 1-Pic-5-N3 thiosialyl donor was designed and synthesized, based on which a new sialylation protocol was established. In comparison to conventional sialylation methods, the new protocol exhibited obvious advantages, including excellent α-stereoselectivity in the absence of a solvent effect, broad substrate scope encompassing the challenging sialyl 8- and 9-hydroxy groups of sialic acid acceptors, flexibility in sialoside derivative synthesis, high temperature tolerance and easy scalability. In particular, the applicability to the synthesis of complex and bioactive N-glycan antennae when combined with the MPEP glycosylation protocol via the “latent-active” strategy has been shown. Mechanistically, the excellent α-stereoselectivity of the novel sialylation protocol could be attributed to the dramatic electron-withdrawing effect of the protonated Pic groups, which was supported by control reactions and DFT calculations.

Original languageEnglish
Pages (from-to)17000-17008
Number of pages9
JournalAngewandte Chemie. International Edition
Issue number47
Publication statusPublished - 18 Nov 2019


  • directing groups
  • glycan antennae
  • glycosylation
  • sialoside
  • stereoselective sialylation


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