Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions

作者：Thomas Hansen, Hidde Elferink, Jacob M. A. van Hengst, Kas J. Houthuijs, Wouter A. Remmerswaal, Alexandra Kromm, Giel Berden, Stefan van der Vorm, Anouk M. Rijs, Herman S. Overkleeft, Dmitri V. Filippov, Floris P. J. T. Rutjes, Gijsbert A. van der Marel, Jonathan Martens, Jos Oomens, Jeroen D. C. Codée, Thomas J. Boltje · 发表于：Nature Communications · 年份：2020 · DOI：10.1038/s41467-020-16362-x · 被引用次数：124 · 研究领域：Carbohydrate Chemistry and Synthesis、Glycosylation and Glycoproteins Research、Genomics and Phylogenetic Studies

Controlling the chemical glycosylation reaction remains the major challenge in the synthesis of oligosaccharides. Though 1,2-trans glycosidic linkages can be installed using neighboring group participation, the construction of 1,2-cis linkages is difficult and has no general solution. Long-range participation (LRP) by distal acyl groups may steer the stereoselectivity, but contradictory results have been reported on the role and strength of this stereoelectronic effect. It has been exceedingly difficult to study the bridging dioxolenium ion intermediates because of their high reactivity and fleeting nature. Here we report an integrated approach, using infrared ion spectroscopy, DFT computations, and a systematic series of glycosylation reactions to probe these ions in detail. Our study reveals how distal acyl groups can play a decisive role in shaping the stereochemical outcome of a glycosylation reaction, and opens new avenues to exploit these species in the assembly of oligosaccharides and glycoconjugates to fuel biological research.