Protecting-group-free <i>S</i>-glycosylation towards thioglycosides and thioglycopeptides in water

Zhang, Gaolan; Gadi, Madhusudhan Reddy; Cui, Xikai; Liu, Ding; Zhang, Jiabin; Saikam, Varma; Gibbons, Christopher; Wang, Peng George; Li, Lei

doi:10.1039/d1gc00098e

Cited by 24 publications

(13 citation statements)

References 55 publications

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“…Although cyano group protected deoxythio sugar fluoride 1 k failed to give glycosylation products due to decomposition, other S ‐protecting groups including trityl (Trt), tert ‐butyl ( t Bu), diphenylmethyl (DPM), para ‐methoxybenzyl (PMB), benzyloxymethyl (BOM), and methoxymethyl (MOM) were tolerated to furnish various S ‐disaccharides in good yields (Scheme 3). Initially, it was found that the decreased solubility [23] of S ‐Trt‐ and S ‐DPM‐protected mannosyl fluorides ( 1 l and 1 n ) in water led to low yields of glycosylation products and significant amounts of disulfide byproducts. Fortunately, this problem was solved by using a mixture of degassed water and methanol as reaction solvent.…”

Section: Resultsmentioning

confidence: 99%

“…Prior to our investigation, this type of transformation for thio‐disaccharides synthesis in water has only been achieved by enzymatic approaches with engineered thioglycosynthases [22] . During the preparation of this manuscript, Li and co‐workers reported the preparation of thio‐oligosaccharides by aqueous glycosylation using glycosyl acceptors under Miller's conditions [23] . However, mainly glycosyl acceptors with a C6‐thiol were employed with one exception.…”

Section: Introductionmentioning

confidence: 99%

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Streamlined Iterative Assembly of Thio‐Oligosaccharides by Aqueous S‐Glycosylation of Diverse Deoxythio Sugars

et al. 2022

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A streamlined iterative assembly of thio‐oligosaccharides was developed by aqueous glycosylation. Facile syntheses of various deoxythio sugars with the sulfur on different positions from commercially available starting materials were described. These syntheses featured efficient chemical methods including our recently reported BTM‐catalyzed site‐selective acylation. The resulting deoxythio sugars could then be used for the Ca(OH)2‐promoted protecting group‐free S‐glycosylation in water at room temperature. The aqueous glycosylation reaction proceeded smoothly to afford the corresponding 1,2‐trans S‐glycosides in good yields with high chemo‐ and stereoselectivity. An appropriate choice of protecting groups for the thiol in the glycosyl donor was necessary for the development of iterative synthesis of thio‐oligosaccharides. The aqueous glycosylation was then applied to the synthesis of a trimannoside moiety of N‐linked glycans core region.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Streamlined Iterative Assembly of Thio‐Oligosaccharides by Aqueous S‐Glycosylation of Diverse Deoxythio Sugars

et al. 2022

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“… 54 Under these conditions, thiols also react with glycosyl fluorides and this has been used in the protection group free synthesis of thioglycosides and thioglycopeptides ( Scheme 6 C). 55 In a very recent and beautiful paper, Fairbanks et al 56 showed that other activation methods also can be used to connect two unprotected monosaccharides ( Scheme 6 D). GlcNAc derivatives can be smoothly converted into oxazolines with DMC and triethylamine.…”

Section: Discussionmentioning

confidence: 99%

“…Using glycosyl fluoride as donors and Ca(OH) 2 as a promotor, tyrosine residues in the peptides glucagon, endomorphin-2, and leu-enkephalin could be modified efficiently . Under these conditions, thiols also react with glycosyl fluorides and this has been used in the protection group free synthesis of thioglycosides and thioglycopeptides (Scheme C) . In a very recent and beautiful paper, Fairbanks et al showed that other activation methods also can be used to connect two unprotected monosaccharides (Scheme D).…”

Section: Discussionmentioning

confidence: 99%

Site-Selective Modification of (Oligo)Saccharides

Witte

Minnaard

2022

ACS Catal.

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Oligosaccharides, either as such or as part of glycolipids, glycopeptides, or glycoproteins, are ubiquitous in nature and fulfill important roles in the living cell. Also in medicine and to some extent in materials, oligosaccharides play an important role. In order to study their function, modifying naturally occurring oligosaccharides, and building in reactive groups and reporter groups in oligosaccharides, are key strategies. The development of oligosaccharides as drugs, or vaccines, requires the introduction of subtle modifications in the structure of oligosaccharides to optimize efficacy and, in the case of antibiotics, circumvent bacterial resistance. Provided the natural oligosaccharide is available, site-selective modification is an attractive approach as total synthesis of the target is often very laborious. Researchers in catalysis areas, such as transition-metal catalysis, enzyme catalysis, organocatalysis, and photoredox catalysis, have made considerable progress in the development of site-selective and late-stage modification methods for mono- and oligosaccharides. It is foreseen that the fields of enzymatic modification of glycans and the chemical modification of (oligo)saccharides will approach and potentially meet each other, but there is a lot to learn and discover before this will be the case.

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“…On the other hand, S -glycoside derivatives have drawn significant attention in recent years. − Thioethers were discovered to enhance biological activities such as antimicrobial and antitumor activity. − As a result, thioglycosides have a high potential as therapeutics and are becoming more popular as pharmaceutical targets . In light of the previous information and our ongoing research into developing new compounds having a thiophene and/or benzothiazole ring as potent drugs, a series of novel benzothiazol-2-yl-5-mercaptothiophene molecules bearing sugar moieties have been synthesized and examined for their cytotoxicity against five normal cells and their reduction percent by a plague reduction assay against five viruses.…”

Section: Introductionmentioning

confidence: 99%

Novel Thiophene Thioglycosides Substituted with the Benzothiazole Moiety: Synthesis, Characterization, Antiviral and Anticancer Evaluations, and NS3/4A and USP7 Enzyme Inhibitions

2022

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Novel derivatives of benzothiazole-2-thiophene Sglycoside were synthesized and tested for their antiviral and anticancer potency and NS3/4A and USP7 enzyme inhibitions. The ring system was formed by first synthesizing new derivatives of 5-mercaptothiophene substituted with the benzothiazole moiety, followed by coupling with various halo sugar derivatives. New compounds were tested in vitro for the cytotoxic effect on five types of normal cell lines and for antiviral activity using a plaque reduction assay against CBV4, HSV-1, HCVcc genotype 4 viruses, HAV HM 175, and HAdV7. Notably, three compounds demonstrated substantial IC 50 , CC 50 , and SI values against HSV-1 with a viral reduction of 80% or more. Two substances have demonstrated a reduction of more than 50% in CBV4 and HCVcc viruses. The effectiveness of the compounds against HSV-1 and HCVcc was tested for their capability to inhibit NS3/4A protease and USP7 enzyme. Additionally, a panel of 60 human cancer cells was used to investigate the ability of the newly synthesized compounds to inhibit the in vitro tumor growth. The results revealed that two compounds, 6a and 6c, have an inhibitory effect on most cancer types, whereas 6d and 6f inhibited only three and two cell lines, respectively.

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Protecting-group-free S-glycosylation towards thioglycosides and thioglycopeptides in water

Abstract: A nature-inspired facile and green S-glycosylation method has been developed featuring protecting-group-free and proceeding in water like enzymatic synthesis. Glycosylation of fluoride donors with thiol sugar acceptors using Ca(OH)2 as...

Cited by 24 publications

References 55 publications

Streamlined Iterative Assembly of Thio‐Oligosaccharides by Aqueous S‐Glycosylation of Diverse Deoxythio Sugars

Streamlined Iterative Assembly of Thio‐Oligosaccharides by Aqueous S‐Glycosylation of Diverse Deoxythio Sugars

Site-Selective Modification of (Oligo)Saccharides

Novel Thiophene Thioglycosides Substituted with the Benzothiazole Moiety: Synthesis, Characterization, Antiviral and Anticancer Evaluations, and NS3/4A and USP7 Enzyme Inhibitions

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