1464-44-4Relevant articles and documents
Isotope studies of the transfer of the carbon atoms of carbohydrate derivatives into aromatic compounds (especially xanthene) under degradation conditions
Ferrier,Severn,Furneaux,Miller
, p. 87 - 94 (1992)
Treatment of various 13C-carbohydrate-labelled phenyl β-D-glucopyranosides at 350°C in aqueous phenol in the presence of zinc chloride, with 13C NMR analysis of the xanthene formed as the major neutral product, indicated that the methylene carbon atom (C-9) of this compound was derived from C-1 (30%), C-2 (20%), and C-6 (50%) of the glucosyl units. In addition, 4.5% of the carbon from the sugar was incorporated into the aromatic rings of the xanthene. Mass spectrometry of the phenol produced on heating methyl α-D-glucopyranoside (50% U-13C) at 350°C for 1 h in aqueous zinc chloride showed the aromatic rings to be derived from the glucosyl moiety, partly without cleavage of the carbon chain and also after cleavage and recombination of the fragments.
Phenyl glycosides – Solid-state NMR, X-ray diffraction and conformational analysis using genetic algorithm
Wa?ejko, Piotr,Bukowicki, Jaros?aw,Dobrzycki, ?ukasz,Socha, Pawe?,Paradowska, Katarzyna
, p. 126 - 136 (2019/01/03)
The X-ray structures of 2,6-dimethylphenyl and phenyl 2,3,4,6-tetra-O-acetyl β-glucosides (1 and 3) and phenyl α-mannoside (6) were obtained. The independent part of the unit cell of the glycosides 1 and 6 was formed by one molecule, and for the glucoside 3, two molecules in the crystal cell were observed. In deacetylated glycosides 4 and 6 the crystal structure was established by a hydrogen bond network formed between the sugar hydroxyls and solvent molecules. The 13C CPMAS NMR spectra of aryl glycosides 1–6 were analysed. In the spectrum of 3, doubling of the C4 aryl signal was observed which confirmed the presence of two independent molecules in the solid sample. The GAAGS (Genetic Algorithm-Assisted Grid Search) method was used to determine the low-energy conformers of α-mannosides and β-glucosides. The orientation of the aryl pendant group was calculated using Molecular Mechanics (MMFF94) as well as Quantum Mechanics theory (DFT, B3LYP/6-31 + G(d,p)).
Rapid phenolic O-glycosylation of small molecules and complex unprotected peptides in aqueous solvent
Wadzinski, Tyler J.,Steinauer, Angela,Hie, Liana,Pelletier, Guillaume,Schepartz, Alanna,Miller, Scott J.
, p. 644 - 652 (2018/05/04)
Glycosylated natural products and synthetic glycopeptides represent a significant and growing source of biochemical probes and therapeutic agents. However, methods that enable the aqueous glycosylation of endogenous amino acid functionality in peptides without the use of protecting groups are scarce. Here, we report a transformation that facilitates the efficient aqueous O-glycosylation of phenolic functionality in a wide range of small molecules, unprotected tyrosine, and tyrosine residues embedded within a range of complex, fully unprotected peptides. The transformation, which uses glycosyl fluoride donors and is promoted by Ca(OH)2, proceeds rapidly at room temperature in water, with good yields and selective formation of unique anomeric products depending on the stereochemistry of the glycosyl donor. High functional group tolerance is observed, and the phenol glycosylation occurs selectively in the presence of virtually all side chains of the proteinogenic amino acids with the singular exception of Cys. This method offers a highly selective, efficient, and operationally simple approach for the protecting-group-free synthesis of O-aryl glycosides and Tyr-O-glycosylated peptides in water.