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

Ge, Jiantao; Zhou, Lang; Luo, Tao; Lv, Jian; Dong, Hai

doi:10.1021/acs.orglett.9b02033

Cited by 20 publications

(28 citation statements)

References 39 publications

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“…H 2 O) in DMF to form per-O-acetylated glycosyl thiols. [15] For this new method, ethyl acetate and BF 3 • Et 2 O can be easily removed by distillation so that the resulting glycosyl thioacetates can be easily trans- ferred into DMF. Based on these, we envisioned that glycosyl disulfides and thiols be efficiently synthesized starting from corresponding per-O-acetylated glycoses through a two-step reaction without the need to isolate the intermediate products, glycosyl thioacetates.…”

Section: Resultsmentioning

confidence: 99%

Improved Synthesis of 1‐Glycosyl Thioacetates and Its Application in the Synthesis of Thioglucoside Gliflozin Analogues

Feng

Wang

et al. 2021

Eur J Org Chem

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An improved method to synthesize 1-glycosyl thioacetates was developed, where per-O-acetylated glycoses were allowed to directly react with potassium thioacetate (KSAc) in the presence of BF 3 • Et 2 O in ethyl acetate under mild conditions. This method not only overcomes the disadvantage of the traditional onestep method, which is that the odorous and toxic thioacetic acid has to be used, but also overcomes the disadvantage of the traditional two-step method, which is that the unstable intermediate, glycosyl halide, has to be synthesized from the per-O-acetylated glycose in advance. Based on this, the per-O-acetylated glucosyl disulfide and the per-O-acetylated glucosyl 1-thiol were efficiently synthesized in high yields (91 % and 90 % respectively) starting from per-O-acetylated glycoses in two-step without the need to isolate intermediate products.Through metal-catalyzed cross-coupling of per-O-acetylated glucosyl 1-thiol with aryl-iodide under very mild conditions, two thioglucoside gliflozin analogues were efficiently synthesized in high yields for the first time. These two thioglucoside gliflozin analogues were further confirmed to be stable to hydrolysis of β-glucosidase.

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Section: Resultsmentioning

confidence: 99%

Improved Synthesis of 1‐Glycosyl Thioacetates and Its Application in the Synthesis of Thioglucoside Gliflozin Analogues

Feng

Wang

et al. 2021

Eur J Org Chem

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“…In our previous studies on the synthesis of deoxyglycosides by desulfurization under UV light (Ge et al, 2017b(Ge et al, , 2019, we didn't obtain 4-deoxymannosidic derivatives because we were unable to obtain 4-SAc mannosides efficiently. With 4-SAc mannosides 5 and 6 in the hands, 4-deoxymannosidic derivatives 46 and 47 were obtained in 81 and 79% yields by our one-pot method removing thioacetate group (Figure 2), respectively.…”

Section: Resultsmentioning

confidence: 99%

“…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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“…Among them, the use of glycosyl donors containing C‐2 thioacetate (SAc) in glycosylation for exclusive α/β‐stereoselectivity, followed by desulfurization to obtain 2‐deoxyglycosides, has been fully demonstrated [2] . A method of efficient ultraviolet light‐induced desulfurization developed by us makes the advantage of thioacetate as a temporary guiding group for the synthesis of 2‐deoxyglycosides more obvious [2b,c,3] . However, a big challenge for this strategy is how to efficiently obtain 2‐SAc glycosyl donors.…”

Section: Introductionmentioning

confidence: 99%

Efficient Preparation of 2‐SAc‐Glycosyl Donors and Investigation of Their Application in the Synthesis of 2‐Deoxyglycosides

et al. 2022

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In this study, we have developed efficient strategies for the synthesis of glycosyl donors with 2-thioacetyl (SAc) groups in order to synthesize 2-deoxysugars with exclusive α/β-configuration. Starting from free methyl glycosides, four methyl 2-SAc glycosides were synthesized with high efficiency mainly through the double serial inversion strategy, and further turned into four corresponding 1-OAc, 2-SAc α-glycosyl donors (manno-, gluco-, galacto-and talo-types) and four corresponding 1-STol, 2-SAc 1,2-cis-glycosyl donors (manno-, gluco-, galacto-and talo-types). Glycosylation of the 1-OAc, 2-SAc donors and further 2-deoxysugar synthesis have also been investigated in this study.

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

Cited by 20 publications

References 39 publications

Improved Synthesis of 1‐Glycosyl Thioacetates and Its Application in the Synthesis of Thioglucoside Gliflozin Analogues

Improved Synthesis of 1‐Glycosyl Thioacetates and Its Application in the Synthesis of Thioglucoside Gliflozin Analogues

Improved Synthesis of Sulfur-Containing Glycosides by Suppressing Thioacetyl Migration

Efficient Preparation of 2‐SAc‐Glycosyl Donors and Investigation of Their Application in the Synthesis of 2‐Deoxyglycosides

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