The Pyranoside-into-Furanoside Rearrangement of Alkyl Glycosides: Scope and Limitations

Krylov, Vadim B.; Argunov, Dmitry A.; Vinnitskiy, Dmitry Z.; Gerbst, Alexey G.; Ustyuzhanina, Nadezhda E.; Dmitrenok, Andrey S.; Nifantiev, Nikolay E.

doi:10.1055/s-0035-1561595

Cited by 24 publications

(9 citation statements)

References 11 publications

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“…In case of overlapping signals J coupling constants were extracted from 2nd order spectra simulations using Bruker TopSpin software (DAISY). The obtained results (see Tables 1–3) showed good coincidence with previously published data for related monosaccharides [15,26–27].…”

Section: Resultssupporting

confidence: 90%

Influence of per-O-sulfation upon the conformational behaviour of common furanosides

Gerbst

Krylov

Argunov

et al. 2019

Beilstein J. Org. Chem.

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The studies on the recently discovered pyranoside-into-furanoside rearrangement have led us to conformational investigations of furanosides upon their total sulfation. Experimental NMR data showed that in some cases drastic changes of the ring conformation occurred while sometimes only the conformation of the exocyclic C4–C5 linkage changed. Herein we describe a combined quantum chemical and NMR conformational investigation of three common monosaccharide furanosides as their propyl glycosides: α-mannose, β-glucose and β-galactose. Full exploration of the furanoside ring by means of ab initio calculations was performed and coupling constants were calculated for each of the low-energy conformers. The results demonstrated preferred trans-orientation of H4–H5 protons in the non-sulfated molecules which changed to gauche-orientation upon sulfation. The effect is less pronounced in the galactosides. For all the studied structures changes in the conformational distribution were revealed by quantum mechanical calculations, that explained the observed changes in intraring coupling constants occurring upon introduction of sulfates.

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Section: Resultssupporting

confidence: 90%

Influence of per-O-sulfation upon the conformational behaviour of common furanosides

Gerbst

Krylov

Argunov

et al. 2019

Beilstein J. Org. Chem.

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“…Thus, allyl galactoside 5 and allyl fucoside 8 under PIF rearrangement conditions give corresponding furanosides 7 and 9, and no traces of the initially formed per-O-sulfated allyl pyranosides 6 and 10 were detected in the reaction mixture after 24 h (Table 1, entries 1− 2). 9 On the other hand, propyl αand β-mannopyranosides 11 and 14 under the same conditions gave only per-O-sulfated pyranosides 12 and 15, and no traces of proposed furanoside products 13 and 16 were found. The behavior of these mannosides is probably determined by the axial orientation of the OH group at C-2.…”

Section: ■ Results and Discussionmentioning

confidence: 88%

“…To determine if this was due to thermodynamic or kinetical reasons, in the present work, a more reactive propyl β- d -glucopyranoside ( 17 ) was used, as the relative rate of the PIF rearrangement of propyl glycosides was shown to be generally higher. 7 Indeed, during 24 h, the initially formed fully O-sulfated propyl β- d -glucopyranoside 19 was consumed to give furanoside 18 in 75% NMR yield.…”

Section: Results and Discussionmentioning

confidence: 99%

“…15 In our previous investigations, the kinetic aspects of PIF rearrangements were studied, including ab initio calculations of the activation energies of monosaccharides with gluco, galacto, fuco, and manno configurations. 8,9 Additionally, there was a study by Satoh et al reporting the importance of the conformational strain caused by protecting groups for the endocyclic cleavage reaction. 16 In this work, we studied the energetic aspects of PIF rearrangements, which revealed for the first time the driving force of the nontrivial chemical process of ring contraction.…”

Section: ■ Introductionmentioning

confidence: 99%

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Driving Force of the Pyranoside-into-Furanoside Rearrangement

et al. 2019

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Ab initio calculations of fully O-sulfated model monosaccharides, including common hexoses (glucose, galactose, fucose, and mannose) and pentoses (arabinose and xylose), were performed to study the energetic properties of the recently discovered pyranoside-into-furanoside (PIF) rearrangement. It was shown that the per-O-sulfated derivatives of furanoside isomers generally had lower energies than the corresponding per-O-sulfated pyranosides, while nonsulfated furanosides were always less favored than nonsulfated pyranosides. Mannose, which is known to be unreactive in PIF rearrangement, was the only exception. The results of the theoretical calculations were confirmed by experimental studies of monosaccharide models and explained the driving force of such unusual ring contraction process as PIF rearrangement. The conclusions of performed investigation can be used for prediction of new substrates applicability for PIF rearrangement.

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“…The synthesis of the corresponding protected furanose isomer 17b was investigated starting from the pyranose derivatives. Many excellent pyranose-to-furanose isomerisation protocols have been reported, [45][46][47][48][49][50] which unfortunately are not all applicable starting from 16a due to the presence of the vicinal fluorine motif at C2 and C3. We first envisaged to obtain the furanose 17b following an acetylation/isomerisation precedent with 2-deoxy-2fluorogalactose 21 from Liu and co-workers (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%