Synthesis of Deoxyglycosides by Desulfurization under UV Light

Ge, Jiantao; Li, Yingying; Tian, Jun; Liao, Rong‐Zhen; Dong, Hai

doi:10.1021/acs.joc.7b00896

Cited by 28 publications

(34 citation statements)

References 64 publications

(104 reference statements)

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“…1−15 Usually, these deoxy carbohydrate derivatives were synthesized through the reduction of glycals, 16 glyco-epoxides, 17 glycosides with halides, 18−24 and glycosides with a thiocarbonyl group 25−30 and thioacetate group. 31,32 Recently, we have developed a method to obtain the deoxyglycosides through desulfurization of glycoside thiols under ultraviolet light (Scheme 1a) 33 in order to overcome the shortcomings of Raney nickel catalyzed reduction of a thioacetate group. 31,32 In this method, the acylated substrates have to be deprotected in the first step to form glycosyl thiols, which is then desulfurized in the second step to form unprotected deoxy glycosides.…”

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confidence: 99%

“…We next performed experiments under the optimized conditions (Figure 2 starting from free methyl glycopyranosides in 2−3 steps with total yields of 60−75% according to our previously reported methods. 33,34,38 The substrates were treated with 1.8 equiv of N 2 H 4 •H 2 O in DMF at room temperature. By TLC plate, it was observed that the deacetylation of the thioacetate for all the substrates could be completed within 2−5 min.…”

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confidence: 99%

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A One-Pot Method for Removal of Thioacetyl Group via Desulfurization under Ultraviolet Light To Synthesize Deoxyglycosides

Zhou

Luo

et al. 2019

Org. Lett.

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We herein developed an efficient method for removing thioacetyl to synthesize acylated deoxy glycosides in a one-pot reaction, where the thioacetyl was selectively deacetylated by hydrazine hydrate in DMF within 2–5 min at room temperature, followed by desulfurization under UV light for 1–2 h in the presence of TCEP·HCl. The method was then used to synthesize 2-deoxy glycosides with absolute α/β-configuration via stereoselective control of C-2 thioacetate in glycosylation.

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A One-Pot Method for Removal of Thioacetyl Group via Desulfurization under Ultraviolet Light To Synthesize Deoxyglycosides

Zhou

Luo

et al. 2019

Org. Lett.

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“…Diverse methods have been used for synthesizing deoxygenated mimetics [91]. Deoxygenated derivatives have also been widely used in activity studies to gain structural information on the importance of different OH groups in receptor binding [92,93].…”

Section: Replacement Of Oh Functional Groupsmentioning

confidence: 99%

Bioisosteres of Carbohydrate Functional Groups in Glycomimetic Design

Hevey

2019

Biomimetics

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The aberrant presentation of carbohydrates has been linked to a number of diseases, such as cancer metastasis and immune dysregulation. These altered glycan structures represent a target for novel therapies by modulating their associated interactions with neighboring cells and molecules. Although these interactions are highly specific, native carbohydrates are characterized by very low affinities and inherently poor pharmacokinetic properties. Glycomimetic compounds, which mimic the structure and function of native glycans, have been successful in producing molecules with improved pharmacokinetic (PK) and pharmacodynamic (PD) features. Several strategies have been developed for glycomimetic design such as ligand pre-organization or reducing polar surface area. A related approach to developing glycomimetics relies on the bioisosteric replacement of carbohydrate functional groups. These changes can offer improvements to both binding affinity (e.g., reduced desolvation costs, enhanced metal chelation) and pharmacokinetic parameters (e.g., improved oral bioavailability). Several examples of bioisosteric modifications to carbohydrates have been reported; this review aims to consolidate them and presents different possibilities for enhancing core interactions in glycomimetics.

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“…sulfur-containing glycosides (Ge et al, 2017a(Ge et al, , 2019. The efficiency of obtaining siteselective sulfur-containing glycosides is the key to this approach (Ge et al, 2017a,b).…”

Section: Introductionmentioning

confidence: 99%

Improved Synthesis of Sulfur-Containing Glycosides by Suppressing Thioacetyl Migration

Luo

Zhang

et al. 2020

Front. Chem.

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Complex mixtures were often observed when we attempted to synthesize 4-thio-and 2,4-dithio-glycoside derivatives by double parallel and double serial inversion, thus leading to no or low yields of target products. The reason was later found to be that many unexpected side products were produced when a nucleophile substituted the leaving group on the substrate containing the thioacetate group. We hypothesized that thioacetyl migration is prone to occur due to the labile thioacetate group even under weak basic conditions caused by the nucleophile, leading to this result. Therefore, we managed to inhibit the generation of thiol groups from thioacetate groups by the addition of an appropriate amount of conjugate acid/anhydride, successfully improving the synthesis of 4-thio-and 2,4-dithio-glycoside derivatives. The target products which were previously difficult to synthesize, were herein obtained in relatively high yields. Finally, 4-deoxy-and 2,4-dideoxy-glycoside derivatives were efficiently synthesized through the removal of thioacetate groups under UV light, starting from 4-thio-and 2,4-dithio-glycoside derivatives.

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Synthesis of Deoxyglycosides by Desulfurization under UV Light

Cited by 28 publications

References 64 publications

A One-Pot Method for Removal of Thioacetyl Group via Desulfurization under Ultraviolet Light To Synthesize Deoxyglycosides

A One-Pot Method for Removal of Thioacetyl Group via Desulfurization under Ultraviolet Light To Synthesize Deoxyglycosides

Bioisosteres of Carbohydrate Functional Groups in Glycomimetic Design

Improved Synthesis of Sulfur-Containing Glycosides by Suppressing Thioacetyl Migration

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