Direct Synthesis of <i>para</i>-Nitrophenyl Glycosides from Reducing Sugars in Water

Qiu, Xin; Fairbanks, Antony J.

doi:10.1021/acs.orglett.0c00728

Cited by 22 publications

(9 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, the application of glycosyltransferases is still hampered by the high cost of the activated sugars required as glycosylation donors. On the contrary, nitrophenyl-sugars are more cost-effective donors, easier to handle, and synthesize 76 , which implies an advantage of rBxTW1-E495A over glycosyltransferases as a versatile synthetic biotool. The development of strategies of enzyme immobilization and recycling will probably be the next steps to improve the cost-effectiveness of the developed biotool.…”

Section: Discussionmentioning

confidence: 99%

Thioglycoligase derived from fungal GH3 β-xylosidase is a multi-glycoligase with broad acceptor tolerance

et al. 2020

View full text Add to dashboard Cite

The synthesis of customized glycoconjugates constitutes a major goal for biocatalysis. To this end, engineered glycosidases have received great attention and, among them, thioglycoligases have proved useful to connect carbohydrates to non-sugar acceptors. However, hitherto the scope of these biocatalysts was considered limited to strong nucleophilic acceptors. Based on the particularities of the GH3 glycosidase family active site, we hypothesized that converting a suitable member into a thioglycoligase could boost the acceptor range. Herein we show the engineering of an acidophilic fungal β-xylosidase into a thioglycoligase with broad acceptor promiscuity. The mutant enzyme displays the ability to form O-, N-, S- and Se- glycosides together with sugar esters and phosphoesters with conversion yields from moderate to high. Analyses also indicate that the pKa of the target compound was the main factor to determine its suitability as glycosylation acceptor. These results expand on the glycoconjugate portfolio attainable through biocatalysis.

show abstract

Section: Discussionmentioning

confidence: 99%

Thioglycoligase derived from fungal GH3 β-xylosidase is a multi-glycoligase with broad acceptor tolerance

et al. 2020

View full text Add to dashboard Cite

show abstract

“…phenols like o-or p-nitrophenol. 42,43 Since hydroxyazobenzenes are more acidic than phenol, we decided to study the DMC-mediated glycosylation reaction of DHABs with unprotected sugars in aqueous solutions (Scheme 1d).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Glycosylation with unprotected sugars in aqueous media is not trivial. , Recently, 2-chloro-1,3-dimethylimidazolinium chloride (DMC) has been successfully used as a dehydrative condensing agent to synthesize 2-pyridyl 1-thioglycosides or phenyl-β- O -glycosides , by a reaction of unprotected sugar with respectively 2-mercaptopyridine or phenol derivatives under basic aqueous conditions . It has been shown that good yields (up to 84%) can be obtained with relatively acidic phenols like o - or p -nitrophenol. , Since hydroxyazobenzenes are more acidic than phenol, we decided to study the DMC-mediated glycosylation reaction of DHABs with unprotected sugars in aqueous solutions (Scheme d).…”

Section: Introductionmentioning

confidence: 99%

One-Pot Synthesis of Water-Soluble Glycosyl Azobenzenes and Their Photoswitching Properties in Water

2022

View full text Add to dashboard Cite

Molecular photoswitches capable of reversible photoswitching in aqueous media are highly demanded for various biological applications and photopharmacology. Carbohydrates, as natural and abundant raw materials, provide opportunity to make photoswitches water-soluble through linking sugar to the photoswitching molecules. We have developed a one-pot synthesis method to prepare water-soluble glycosyl azobenzenes through DMC (2-chloro-1,3-dimethylimidazolinium chloride)-mediated glycosylation between sugar and dihydroxyazobenzenes (DHABs) in aqueous media. The scope of the method has been investigated with different mono- and disaccharides, as well as with p,p′- and o,o′-DHAB, with excellent 1,2-trans stereoselectivity. Diglycosylation products can also be obtained with an excess amount of monosaccharides in one step. We have also demonstrated the possibility of further functionalization on the azobenzene moiety of glycosyl azobenzene. Both mono- and diglycosyl azobenzenes showed excellent photoswitching properties in water with high fatigue resistance and good thermostability for the Z-isomers. Excellent E → Z photoisomerization of both mono- and diglycosylated azobenzenes (Z/E = 99/1) is observed under illumination at 365 nm, while back Z → E photoisomerization can be achieved with blue light (with E/Z = 80/20 at PSS485 for the diglycosyl derivative).

show abstract

“…Notably, an aqueous activation of anomeric hydroxy groups using 2‐chloro‐1,3‐dimethylimidazolinium chloride (DMC) as dehydrating reagent was reported by Shoda and co‐workers. Thus, 1,6‐anhydrosugars, [14] glycosyl oxazolines, [15] glycosyl azides, [16] thioglycosides, [17] and para ‐nitrophenyl glycosides [18] can be synthesized in one step from unprotected sugars in aqueous solutions (Scheme 1b). Recently, Miller and co‐workers [19] reported a site‐selective aqueous glycosylation of unprotected sucrose and analogues using glycosyl fluorides as donors in the presence of calcium ion.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2022

View full text Add to dashboard Cite

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.

show abstract

Direct Synthesis of para-Nitrophenyl Glycosides from Reducing Sugars in Water

Cited by 22 publications

References 27 publications

Thioglycoligase derived from fungal GH3 β-xylosidase is a multi-glycoligase with broad acceptor tolerance

Thioglycoligase derived from fungal GH3 β-xylosidase is a multi-glycoligase with broad acceptor tolerance

One-Pot Synthesis of Water-Soluble Glycosyl Azobenzenes and Their Photoswitching Properties in Water

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

Contact Info

Product

Resources

About