2492-87-7Relevant articles and documents
Single-crystal and powder X-ray diffraction and solid-state 13C NMR of p-nitrophenyl glycopyranosides, the derivatives of d-galactose, d-glucose, and d-mannose
Gubica, Tomasz,Temeriusz, Andrzej,Paradowska, Katarzyna,Ostrowski, Andrzej,Klimentowska, Paulina,Cyranski, Michal K.
, p. 1734 - 1744 (2009)
The X-ray diffraction patterns, 13C CP MAS NMR spectra, and powder X-ray diffraction analyses were obtained for selected p-nitrophenyl glycosides: α- and β-d-galactopyranosides (1 and 2), α- and β-d-glucopyranosides (3 and 4), and α- and β-d-mannopyranosides (5 and 6). In X-ray diffraction analysis of 1 and 2, characteristic shortening and lengthening of selected bonds were observed in the molecules of 1 due to anomeric effect, and in the crystal lattice of 1 and 2, hydrogen bonds of complex network were detected. In the crystal asymmetric unit of 1 there were two independent molecules, whereas in 2 there was one molecule. For 1 and 3-6 the number of resonances in solid-state 13C NMR spectra exceeded the number of the carbon atoms in the molecules, while for 2 there were distinct singlet resonances in its solid-state NMR spectrum. Furthermore, the powder X-ray diffraction (PXRD) performed for 1-3 and 5 revealed that 1, 3, and 5 existed as single polymorphs proving that the doublets observed in appropriate solid-state NMR spectra were connected with two non-equivalent molecules in the crystal asymmetric unit. On the other hand 2 existed as a mixture of two polymorphs, one of them was almost in agreement with the calculated pattern obtained from XRD (the difference in volumes of the unit cells), and the subsequent unknown polymorph existed in small amounts and therefore it was not observed in solid-state NMR measurements.
Controllable Iterative β-Glucosylation from UDP-Glucose by Bacillus cereus Glycosyltransferase GT1: Application for the Synthesis of Disaccharide-Modified Xenobiotics
Jung, Jihye,Nidetzky, Bernd,Schachtschabel, Doreen,Speitling, Michael
, p. 14630 - 14642 (2021/12/09)
Glycosylation in natural product metabolism and xenobiotic detoxification often leads to disaccharide-modified metabolites. The chemical synthesis of such glycosides typically separates the glycosylation steps in space and time. The option to perform the two-step glycosylation in one pot, and catalyzed by a single permissive enzyme, is interesting for a facile access to disaccharide-modified products. Here, we reveal the glycosyltransferase GT1 from Bacillus cereus (BcGT1; gene identifier: KT821092) for iterative O-β-glucosylation from uridine 5′-diphosphate (UDP)-glucose to form a β-linked disaccharide of different metabolites, including a C15 hydroxylated detoxification intermediate of the agricultural herbicide cinmethylin (15HCM). We identify thermodynamic and kinetic requirements for the selective formation of the disaccharide compared to the monosaccharide-modified 15HCM. As shown by NMR and high-resolution MS, β-cellobiosyl and β-gentiobiosyl groups are attached to the aglycone's O15 in a 2:1 ratio. Glucosylation reactions on methylumbelliferone and 4-nitrophenol involve reversible glycosyl transfer from and to UDP as well as UDP-glucose hydrolysis, both catalyzed by BcGT1. Collectively, this study delineates the iterative β-d-glucosylation of aglycones by BcGT1 and demonstrates applicability for the programmable one-pot synthesis of disaccharide-modified 15HCM.
Direct Synthesis of para-Nitrophenyl Glycosides from Reducing Sugars in Water
Fairbanks, Antony J.,Qiu, Xin
supporting information, (2020/03/24)
Reducing sugars may be directly converted into the corresponding para-nitrophenyl (pNP) glycosides using 2-chloro-1,3-dimethylimidazolinium chloride (DMC), para-nitrophenol, and a suitable base in aqueous solution. The reaction is stereoselective for sugars with either a hydroxyl or an acetamido group at position 2, yielding the 1,2-trans pNP glycosides. A judicious choice of base allows extension to di-and oligosaccharide substrates, including a complex N-glycan oligosaccharide isolated from natural sources, without the requirement of any protecting group manipulations
