Directing effect by remote electron-withdrawing protecting groups at O-3 or O-4 position of donors in glucosylations and galactosylations

Baek, Ju Yuel; Kwon, Hea-Won; Myung, Se Jin; Park, Jung Jun; Kim, Mi Young; Rathwell, Dominea C. K.; Jeon, Heung Bae; Seeberger, Peter H.; Kim, Kwan Soo

doi:10.1016/j.tet.2015.06.014

Cited by 39 publications

(36 citation statements)

References 33 publications

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“…The sulfonyl protecting group, initially explored as a strongly electron-withdrawing group at the 2-position capable of stabilizing manno- and rhamnopyranosyl triflates and other sulfonates, 71−73 and subsequently employed with varying degrees of success at the 4-position of 2,6-dideoxyglycopyranosyl donors, 74 and at the 3-, 4-, and 6-positions of other pyranosyl donors, 75,76 does not change the population of the side chain when replacing a benzyl ether at the 4-position of a glucosyl donor (Table 2, Figure 7b). The influence of the 4- O -sulfonyl group on glucopyranosylation can therefore be interpreted solely in terms of the change in electron-withdrawing ability.…”

Section: Discussionmentioning

confidence: 99%

“…76 NMR (600 MHz, CDCl 3 ) δ 7.60–7.58 (m, 2H), 7.42–7.40 (m, 2H), 7.37–7.25 (m, 16H), 5.65 (br s, 1H), 4.78 (d, J = 11.3 Hz, 1H), 4.77 (d, J = 10.3 Hz, 1H), 4.75 (d, J = 10.0 Hz, 1H), 4.71–4.67 (m, 1H), 4.57 (d, J = 11.7 Hz, 1H), 4.50 (d, J = 11.0 Hz, 1H), 4.47 (d, J = 11.7 Hz, 1H), 3.77–3.76 (m, 1H), 3.67–3.66 (m, 2H), 3.64 (dd, J = 9.5, 6.0 Hz, 1H), 3.55 (dd, J = 9.5, 6.7 Hz, 1H), 2.09 (s, 3H). 1 H NMR (600 MHz, C 6 D 6 ) δ 7.65–7.61 (m, 2H), 7.39 (t, J = 7.6 Hz, 2H), 7.31 (d, J = 7.3 Hz, 2H), 7.25 (d, J = 7.4 Hz, 2H), 7.17–7.01 (m, 10H), 6.99–6.91 (m, 2H), 5.58 (dd, J = 3.3, 1.1 Hz, 1H), 4.80 (d, J = 10.7 Hz, 1H), 4.75 (d, J = 10.7 Hz, 1H), 4.66 (d, J = 11.2 Hz, 1H), 4.56 (d, J = 9.7 Hz, 1H), 4.28 (d, J = 11.6 Hz, 2H), 4.17 (d, J = 11.9 Hz, 1H), 3.80 (t, J = 9.5 Hz, 1H), 3.47 (dd, J = 9.4, 6.1 Hz, 1H), 3.42 (dd, J = 9.4, 6.5 Hz, 1H), 3.33 (dd, J = 9.2, 3.3 Hz, 1H), 3.32 (ddd, J = 6.5, 6.1, 1.1 Hz, 1H), 1.65 (s, 3H).…”

Section: Methodsmentioning

confidence: 99%

“…76 1 H NMR (600 MHz, CDCl 3 ) δ 8.01–7.93 (m, 2H), 7.66–7.65 (m, 2H), 7.61–7.59 (m, 1H), 7.47–7.45 (m, 2H), 7.40–7.39 (m, 2H), 7.35–7.22 (m, 16H), 5.91 (d, J = 3.0 Hz 1H), 4.87 (d, J = 11.4 Hz, 1H), 4.74 (br s, 2H), 4.70 (d, J = 9.5 Hz, 1H), 4.54 (d, J = 11.0 Hz, 1H), 4.52 (dd, J = 10.6 Hz, 1H), 4.46 (d, J = 10.6 Hz, 1H), 3.92–3.89 (m, 1H), 3.77 (d, J = 9.2, 3.3 Hz, 1H), 3.72 (t, J = 9.4 Hz, 1H), 3.69 (dd, J = 9.6, 5.8 Hz, 1H), 3.59 (dd, J = 9.6, 6.8 Hz, 1H). 1 H NMR (600 MHz, C 6 D 6 ) δ 8.11 (d, J = 8.1 Hz, 2H), 7.70 (dd, J = 12.2, 5.2 Hz, 2H), 7.39 (d, J = 7.9 Hz, 2H), 7.26 (d, J = 7.9 Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 7.17–6.95 (m, 15H), 5.87 (d, J = 3.1 Hz, 1H), 4.75 (d, J = 11.4 Hz, 1H), 4.72 (d, J = 10.9 Hz, 1H), 4.67 (d, J = 10.9 Hz, 1H), 4.54 (d, J = 9.7 Hz, 1H), 4.31 (d, J = 11.4 Hz, 1H), 4.19 (d, J = 11.8 Hz, 1H), 4.12 (d, J = 11.9 Hz, 1H), 3.83 (t, J = 9.4 Hz, 1H), 3.53 (dd, J = 9.3, 6.1 Hz, 1H), 3.49 (dd, J = 9.3, 6.6 Hz, 1H), 3.42 (t, J = 4.8 Hz, 1H), 3.42–3.40 (m, 1H).…”

Section: Methodsmentioning

confidence: 99%

“…The crude residue was purified by column chromatography over silica gel, eluting with hexane/ethyl acetate (8:2) to obtain 25 (0.008 g, 71%) with spectral data consistent with the literature. 76 1 H NMR (600 MHz, CDCl 3 ) δ 7.98–7.93 (m, 2H), 7.64–7.53 (m, 3H), 7.44–7.04 (m, 20H), 5.29 (dd, J = 10.1, 9.4 Hz, 1H), 4.90 (d, J = 10.2 Hz, 1H), 4.77 (d, J = 9.8 Hz, 1H), 4.75 (d, J = 11.0 Hz, 1H), 4.74 (d, J = 10.2 Hz, 1H), 4.62 (d, J = 11.0 Hz, 1H), 4.49 (d, J = 11.6 Hz, 1H), 4.46 (d, J = 11.6 Hz, 1H), 3.83 (dd, J = 9.4, 8.7 Hz, 1H), 3.79–3.75 (m, 1H), 3.66–3.64 (m, 2H), 3.62 (dd, J = 9.8, 8.7 Hz, 1H). 1 H NMR (600 MHz, C 6 D 6 ) δ 8.07–8.04 (m, 2H), 7.73–7.68 (m, 2H), 7.45–7.42 (m, 2H), 7.27–6.94 (m, 19H), 5.65 (dd, J = 10.0, 9.4 Hz, 1H), 4.89 (d, J = 10.8 Hz, 1H), 4.72 (d, J = 9.8 Hz, 1H), 4.72 (d, J = 11.4 Hz, 1H), 4.62 (d, J = 11.4 Hz, 1H), 4.61 (d, J = 10.8 Hz, 1H), 4.26–4.20 (m, 2H), 3.68 (dd, J = 9.4, 8.6 Hz, 1H), 3.62 (dd, J = 10.7, 2.9 Hz, 1H), 3.58 (dd, J = 10.7, 6.0 Hz, 1H), 3.54 (dd, J = 9.8, 8.6 Hz, 1H), 3.48 (ddd, J = 10.0, 6.0, 2.9 Hz, 1H).…”

Section: Methodsmentioning

confidence: 99%

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Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

2018

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The synthesis and conformational analysis of a series of phenyl 2,3,6-tri-O-benzyl-β-d-thio galacto- and glucopyranosides and their 6S-deuterio isotopomers, with systematic variation of the protecting group at the 4-position, are described. For the galactopyranosides, replacement of a 4-O-benzyl ether by a 4-O-alkanoyl or aroyl ester results in a small but measurable shift in side chain population away from the trans,gauche conformation and in favor of the gauche,trans conformer. In the glucopyranoside series on the other hand, replacement of a 4-O-benzyl ether by a 4-O-alkanoyl or aroyl ester results in a small but measurable increase in the population of the trans,gauche conformer at the expense of the gauche,gauche conformer. The possible modulating effect of these conformational changes on the well-known changes in the anomeric reactivity of glycosyl donors as a function of protecting group is discussed, raising the possibility that larger changes may be observed at the transition state for glycosylation. A comparable study with a series of ethyl 2,3,4-tri-O-benzyl-β-d-thioglucopyranosides reveals that no significant influence in side chain population is observed on changing the O6 protecting group.

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Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

2018

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“…Baek et al [134] studied directing effect by remote electron-withdrawing protecting groups at O-3 and O-4 position of donor in glycosylation and galactosylation. Recently, Cox et al [135] and Singh et al [136] investigated participation of different two-substituted ethyl ethers.…”

Section: Mechanistic Investigationsmentioning

confidence: 99%

Recent Advances in NMR Studies of Carbohydrates

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2016

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Catalyst‐Controlled Glycosylation

Levi

Jacobsen

2019

Organic Reactions

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Whereas highly practical chemical methods for the synthesis of polypeptides and polynucleotides are well established and in common use, glycan synthesis remains a challenging endeavor largely reserved for specialists in sugar chemistry. Glycosylation reactions are fundamentally challenging relative to peptide and nucleotide couplings, which involve non‐stereogenic linkages that are not strongly affected by the identity of the specific reacting partners. Carbohydrate couplings engage highly variable, stereochemically complex, and densely functionalized reacting partners, while generating a new stereocenter in the glycosidic linkage. Glycosylation methods that can be applied easily and broadly would be greatly enabling to research concerning the role of sugars in biological chemistry and medicine. Recent developments in transition‐metal catalysis and organocatalysis have enabled selective glycosylation reactions with catalyst‐controlled stereo‐ and site selectivity, making headway toward the longstanding goal of achieving generality in chemical glycosylation. This chapter highlights seminal examples of catalyst control in glycosylation, focusing on cases wherein catalyst structure and electronics play a demonstrated role in the stereochemical outcome of a glycosylation reaction.

show abstract

Directing effect by remote electron-withdrawing protecting groups at O-3 or O-4 position of donors in glucosylations and galactosylations

Cited by 39 publications

References 33 publications

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

Recent Advances in NMR Studies of Carbohydrates

Catalyst‐Controlled Glycosylation

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