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Characterization of Glycosyl Dioxolenium Ions and Their Role in Glycosylation Reactions

preprint
submitted on 03.12.2019, 15:03 and posted on 11.12.2019, 13:17 by Thomas Hansen, Hidde Elferink, Jacob M.A. van Hengst, Kas Houthuijs, Wouter A. Remmerswaal, Alexandra Kromm, Giel Berden, Stefan van der Vorm, Anouk Rijs, Herman S. Overkleeft, Dmitri Filippov, Floris P. J. T. Rutjes, Gijsbert van der Marel, Jonathan Martens, Jos Oomens, Jeroen D. C. Codée, Thomas Boltje
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 calculations 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

Funding

We gratefully acknowledge the expert technical support by the FELIX staff. Quantum-chemical calculations were performed at the SurfSARA HPC center in Amsterdam; access was provided via NWO-Rekentijd grant 17603 (to J.O.) and 17569 (to T.H. and J.D.C.C.). This work was supported by an ERC‐STG (758913) and NWO VIDI grant awarded to T.J.B. and an ERC-CoG (726072) and NWO VICI (VI.C.182.020) grant awarded to J.D.C.C. We kindly acknowledge Mark Somers for technical support

History

Email Address of Submitting Author

t.boltje@science.ru.nl

Institution

Radboud University

Country

Netherlands

ORCID For Submitting Author

0000-0001-9141-8784

Declaration of Conflict of Interest

NA

Version Notes

Version 1.0

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