Reactivity–Stereoselectivity Mapping for the Assembly of Mycobacterium marinum Lipooligosaccharides

Thomas Hansen; Tim P. Ofman; Joey G.C. Vlaming; Ivan A. Gagarinov; Jessey van Beek; Tessa A. Goté; Jacoba M. Tichem; Gijs Ruijgrok; Herman S. Overkleeft; Dmitri V. Filippov; Gijsbert A. van der Marel; Jeroen D.C. Codée

doi:10.1002/anie.202010280

Reactivity–Stereoselectivity Mapping for the Assembly of Mycobacterium marinum Lipooligosaccharides

Thomas Hansen, Tim P. Ofman, Joey G.C. Vlaming, Ivan A. Gagarinov, Jessey van Beek, Tessa A. Goté, Jacoba M. Tichem, Gijs Ruijgrok, Herman S. Overkleeft, Dmitri V. Filippov, Gijsbert A. van der Marel, Jeroen D.C. Codée^*

^*Corresponding author for this work

Chemistry and Pharmaceutical Sciences

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

The assembly of complex bacterial glycans presenting rare structural motifs and cis-glycosidic linkages is significantly obstructed by the lack of knowledge of the reactivity of the constituting building blocks and the stereoselectivity of the reactions in which they partake. We here report a strategy to map the reactivity of carbohydrate building blocks and apply it to understand the reactivity of the bacterial sugar, caryophyllose, a rare C12-monosaccharide, containing a characteristic tetrasubstituted stereocenter. We mapped reactivity–stereoselectivity relationships for caryophyllose donor and acceptor glycosides by a systematic series of glycosylations in combination with the detection and characterization of different reactive intermediates using experimental and computational techniques. The insights garnered from these studies enabled the rational design of building blocks with the required properties to assemble mycobacterial lipooligosaccharide fragments of M. marinum.

Original language	English
Pages (from-to)	937-945
Number of pages	9
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	2
Early online date	28 Aug 2020
DOIs	https://doi.org/10.1002/anie.202010280
Publication status	Published - 11 Jan 2021

Bibliographical note

Publisher Copyright:
© 2020 The Authors. Published by Wiley-VCH GmbH

Funding

Quantum chemical calculations were performed at the SurfSARA HPC center in Amsterdam; access was provided via NWO‐Rekentijd grant 17569 (to T.H. and J.D.C.C.). This work was supported by 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. Quantum chemical calculations were performed at the SurfSARA HPC center in Amsterdam; access was provided via NWO-Rekentijd grant 17569 (to T.H. and J.D.C.C.). This work was supported by 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.

Funders	Funder number
ERC-Cog
Horizon 2020 Framework Programme	726072
NWO-Rekentijd	17569
Not added	053.70.337

Keywords

density functional calculations
glycosyl cation
glycosylation
reactivity
stereoselectivity

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/anie.202010280

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Hansen, T., Ofman, T. P., Vlaming, J. G. C., Gagarinov, I. A., van Beek, J., Goté, T. A., Tichem, J. M., Ruijgrok, G., Overkleeft, H. S., Filippov, D. V., van der Marel, G. A., & Codée, J. D. C. (2021). Reactivity–Stereoselectivity Mapping for the Assembly of Mycobacterium marinum Lipooligosaccharides. Angewandte Chemie - International Edition, 60(2), 937-945. https://doi.org/10.1002/anie.202010280

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abstract = "The assembly of complex bacterial glycans presenting rare structural motifs and cis-glycosidic linkages is significantly obstructed by the lack of knowledge of the reactivity of the constituting building blocks and the stereoselectivity of the reactions in which they partake. We here report a strategy to map the reactivity of carbohydrate building blocks and apply it to understand the reactivity of the bacterial sugar, caryophyllose, a rare C12-monosaccharide, containing a characteristic tetrasubstituted stereocenter. We mapped reactivity–stereoselectivity relationships for caryophyllose donor and acceptor glycosides by a systematic series of glycosylations in combination with the detection and characterization of different reactive intermediates using experimental and computational techniques. The insights garnered from these studies enabled the rational design of building blocks with the required properties to assemble mycobacterial lipooligosaccharide fragments of M. marinum.",

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author = "Thomas Hansen and Ofman, \{Tim P.\} and Vlaming, \{Joey G.C.\} and Gagarinov, \{Ivan A.\} and \{van Beek\}, Jessey and Got{\'e}, \{Tessa A.\} and Tichem, \{Jacoba M.\} and Gijs Ruijgrok and Overkleeft, \{Herman S.\} and Filippov, \{Dmitri V.\} and \{van der Marel\}, \{Gijsbert A.\} and Cod{\'e}e, \{Jeroen D.C.\}",

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year = "2021",

month = jan,

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doi = "10.1002/anie.202010280",

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Hansen, T, Ofman, TP, Vlaming, JGC, Gagarinov, IA, van Beek, J, Goté, TA, Tichem, JM, Ruijgrok, G, Overkleeft, HS, Filippov, DV, van der Marel, GA & Codée, JDC 2021, 'Reactivity–Stereoselectivity Mapping for the Assembly of Mycobacterium marinum Lipooligosaccharides', Angewandte Chemie - International Edition, vol. 60, no. 2, pp. 937-945. https://doi.org/10.1002/anie.202010280

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AU - Hansen, Thomas

AU - Ofman, Tim P.

AU - Vlaming, Joey G.C.

AU - Gagarinov, Ivan A.

AU - van Beek, Jessey

AU - Goté, Tessa A.

AU - Tichem, Jacoba M.

AU - Ruijgrok, Gijs

AU - Overkleeft, Herman S.

AU - Filippov, Dmitri V.

AU - van der Marel, Gijsbert A.

AU - Codée, Jeroen D.C.

PY - 2021/1/11

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AB - The assembly of complex bacterial glycans presenting rare structural motifs and cis-glycosidic linkages is significantly obstructed by the lack of knowledge of the reactivity of the constituting building blocks and the stereoselectivity of the reactions in which they partake. We here report a strategy to map the reactivity of carbohydrate building blocks and apply it to understand the reactivity of the bacterial sugar, caryophyllose, a rare C12-monosaccharide, containing a characteristic tetrasubstituted stereocenter. We mapped reactivity–stereoselectivity relationships for caryophyllose donor and acceptor glycosides by a systematic series of glycosylations in combination with the detection and characterization of different reactive intermediates using experimental and computational techniques. The insights garnered from these studies enabled the rational design of building blocks with the required properties to assemble mycobacterial lipooligosaccharide fragments of M. marinum.

KW - density functional calculations

KW - glycosyl cation

KW - glycosylation

KW - reactivity

KW - stereoselectivity

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Reactivity–Stereoselectivity Mapping for the Assembly of Mycobacterium marinum Lipooligosaccharides

Abstract

Bibliographical note

Funding

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

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