Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions

Thomas Hansen, Hidde Elferink, Jacob M. A. Hengst, Kas J. Houthuijs, Wouter A. Remmerswaal, Alexandra Kromm, Giel Berden, Stefan Vorm, Anouk M. Rijs, Hermen S. Overkleeft, Dmitri V. Filippov, Floris P. J. T. Rutjes, Gijsbert A. Marel, Jonathan Martens, Jos Oomens (), Jeroen D. C. Codée () and Thomas J. Boltje ()
Additional contact information
Thomas Hansen: Leiden University, Leiden Institute of Chemistry
Hidde Elferink: Radboud University Institute for Molecules and Materials
Jacob M. A. Hengst: Leiden University, Leiden Institute of Chemistry
Kas J. Houthuijs: Radboud University Institute for Molecules and Materials
Wouter A. Remmerswaal: Leiden University, Leiden Institute of Chemistry
Alexandra Kromm: Radboud University Institute for Molecules and Materials
Giel Berden: Radboud University Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7-c
Stefan Vorm: Leiden University, Leiden Institute of Chemistry
Anouk M. Rijs: Radboud University Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7-c
Hermen S. Overkleeft: Leiden University, Leiden Institute of Chemistry
Dmitri V. Filippov: Leiden University, Leiden Institute of Chemistry
Floris P. J. T. Rutjes: Radboud University Institute for Molecules and Materials
Gijsbert A. Marel: Leiden University, Leiden Institute of Chemistry
Jonathan Martens: Radboud University Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7-c
Jos Oomens: Radboud University Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7-c
Jeroen D. C. Codée: Leiden University, Leiden Institute of Chemistry
Thomas J. Boltje: Radboud University Institute for Molecules and Materials

Nature Communications, 2020, vol. 11, issue 1, 1-9

Abstract: Abstract 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.

Date: 2020
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DOI: 10.1038/s41467-020-16362-x

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