Remote Participation During Glycosylation Reactions of Galactose Building Blocks: Direct Evidence from Cryogenic Vibrational Spectroscopy

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2020 Jan 17

PMID 31944510

Citations 34

Authors

Mateusz Marianski

Eike Mucha

Kim Greis

Sooyeon Moon

Alonso Pardo

Carla Kirschbaum

Daniel A Thomas

Gerard Meijer

Gert von Helden

Kerry Gilmore

Peter H Seeberger

Kevin Pagel

Affiliations

Soon will be listed here.

Abstract

The stereoselective formation of 1,2-cis-glycosidic bonds is challenging. However, 1,2-cis-selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive owing to their short-lived nature. Herein, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α-selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium-type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2-cis-glycosidic bonds.

Citing Articles

Elucidating reactive sugar-intermediates by mass spectrometry.

Chang C, Wehner D, Prabhu G, Moon E, Safferthal M, Bechtella L Commun Chem. 2025; 8(1):67.

PMID: 40055429 PMC: 11889121. DOI: 10.1038/s42004-025-01467-5.

The effect of neighbouring group participation and possible long range remote group participation in glycosylation.

Das R, Mukhopadhyay B Beilstein J Org Chem. 2025; 21:369-406.

PMID: 39996165 PMC: 11849559. DOI: 10.3762/bjoc.21.27.

Stereoelectronic Effect of Protecting Groups on the Stability of Galactosyl Donor Intermediates.

Kwok R, Rutkoski R, Nagorny P, Marianski M Molecules. 2025; 30(2).

PMID: 39860088 PMC: 11767833. DOI: 10.3390/molecules30020218.

Mechanism of C-3 Acyl Neighboring Group Participation in Mannuronic Acid Glycosyl Donors.

de Kleijne F, Moons P, Ter Braak F, Almizori H, Jakobs L, Houthuijs K J Am Chem Soc. 2024; 147(1):932-944.

PMID: 39692559 PMC: 11726434. DOI: 10.1021/jacs.4c13910.

Mechanistic insight into benzylidene-directed glycosylation reactions using cryogenic infrared spectroscopy.

Chang C, Greis K, Prabhu G, Wehner D, Kirschbaum C, Ober K Nat Synth. 2024; 3(11):1377-1384.

PMID: 39524531 PMC: 11549046. DOI: 10.1038/s44160-024-00619-0.

References

Gonzalez Florez A, Mucha E, Ahn D, Gewinner S, Schollkopf W, Pagel K . Charge-Induced Unzipping of Isolated Proteins to a Defined Secondary Structure. Angew Chem Int Ed Engl. 2016; 55(10):3295-9. PMC: 4770441. DOI: 10.1002/anie.201510983. View

Yao D, Liu Y, Yan S, Li Y, Hu C, Ding N . Evidence of robust participation by an equatorial 4-O group in glycosylation on a 2-azido-2-deoxy-glucopyranosyl donor. Chem Commun (Camb). 2017; 53(20):2986-2989. DOI: 10.1039/c7cc00274b. View

Elferink H, Severijnen M, Martens J, Mensink R, Berden G, Oomens J . Direct Experimental Characterization of Glycosyl Cations by Infrared Ion Spectroscopy. J Am Chem Soc. 2018; 140(19):6034-6038. PMC: 5958338. DOI: 10.1021/jacs.8b01236. View

Lebedel L, Arda A, Martin A, Desire J, Mingot A, Aufiero M . Structural and Computational Analysis of 2-Halogeno-Glycosyl Cations in the Presence of a Superacid: An Expansive Platform. Angew Chem Int Ed Engl. 2019; 58(39):13758-13762. DOI: 10.1002/anie.201907001. View

Chatterjee S, Moon S, Hentschel F, Gilmore K, Seeberger P . An Empirical Understanding of the Glycosylation Reaction. J Am Chem Soc. 2018; 140(38):11942-11953. DOI: 10.1021/jacs.8b04525. View

Grimme S, Antony J, Ehrlich S, Krieg H . A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. 2010; 132(15):154104. DOI: 10.1063/1.3382344. View

Neese F, Valeev E . Revisiting the Atomic Natural Orbital Approach for Basis Sets: Robust Systematic Basis Sets for Explicitly Correlated and Conventional Correlated ab initio Methods?. J Chem Theory Comput. 2015; 7(1):33-43. DOI: 10.1021/ct100396y. View

Crich D, Dai Z, Gastaldi S . On the Role of Neighboring Group Participation and Ortho Esters in β-Xylosylation: C NMR Observation of a Bridging 2-Phenyl-1,3-dioxalenium Ion. J Org Chem. 2021; 64(14):5224-5229. DOI: 10.1021/jo990424f. View

Tkatchenko A, Scheffler M . Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data. Phys Rev Lett. 2009; 102(7):073005. DOI: 10.1103/PhysRevLett.102.073005. View

10.

Bohe L, Crich D . A propos of glycosyl cations and the mechanism of chemical glycosylation; the current state of the art. Carbohydr Res. 2014; 403:48-59. PMC: 4281519. DOI: 10.1016/j.carres.2014.06.020. View

11.

Hill A, Reilly P . Puckering coordinates of monocyclic rings by triangular decomposition. J Chem Inf Model. 2007; 47(3):1031-5. DOI: 10.1021/ci600492e. View

12.

Mucha E, Gonzalez Florez A, Marianski M, Thomas D, Hoffmann W, Struwe W . Glycan Fingerprinting via Cold-Ion Infrared Spectroscopy. Angew Chem Int Ed Engl. 2017; 56(37):11248-11251. DOI: 10.1002/anie.201702896. View

13.

Kim J, Yang H, Boons G . Stereoselective glycosylation reactions with chiral auxiliaries. Angew Chem Int Ed Engl. 2005; 44(6):947-9. DOI: 10.1002/anie.200461745. View

14.

Jung K, Muller M, Schmidt R . Intramolecular o-glycoside bond formation. Chem Rev. 2001; 100(12):4423-42. DOI: 10.1021/cr990307k. View

15.

Mucha E, Marianski M, Xu F, Thomas D, Meijer G, von Helden G . Unravelling the structure of glycosyl cations via cold-ion infrared spectroscopy. Nat Commun. 2018; 9(1):4174. PMC: 6177480. DOI: 10.1038/s41467-018-06764-3. View

16.

Supady A, Blum V, Baldauf C . First-Principles Molecular Structure Search with a Genetic Algorithm. J Chem Inf Model. 2015; 55(11):2338-48. DOI: 10.1021/acs.jcim.5b00243. View

17.

Nigudkar S, Demchenko A . Stereocontrolled 1,2- glycosylation as the driving force of progress in synthetic carbohydrate chemistry. Chem Sci. 2015; 6(5):2687-2704. PMC: 4465199. DOI: 10.1039/C5SC00280J. View

18.

Adero P, Amarasekara H, Wen P, Bohe L, Crich D . The Experimental Evidence in Support of Glycosylation Mechanisms at the S1-S2 Interface. Chem Rev. 2018; 118(17):8242-8284. PMC: 6135681. DOI: 10.1021/acs.chemrev.8b00083. View

19.

Plante O, Palmacci E, Seeberger P . Automated solid-phase synthesis of oligosaccharides. Science. 2001; 291(5508):1523-7. DOI: 10.1126/science.1057324. View

20.

Hahm H, Hurevich M, Seeberger P . Automated assembly of oligosaccharides containing multiple cis-glycosidic linkages. Nat Commun. 2016; 7:12482. PMC: 5025749. DOI: 10.1038/ncomms12482. View