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A wide variety of thioglycosides 1 are selectively hydrolyzed to the corresponding 1-hydroxy sugars 2 in good yields at 0-5 deg C, by employing V2O5-H2O2 catalyzed oxidation of ammonium bromide in CH2Cl2-H2O solvent system. The methodology is very mild, environmentally benign, efficient and highly chemoselective. No side reactions such as bromination either at the anomeric position or double bond or oxidation at the sulfur are encountered.

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Tetrahydropyran – Wikipedia,
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A simple and efficient strategy for the selective modification of the peptide N terminus with an unnatural amino acid is described. A peptide having a SUMO-HisTag-TEV sequence (SUMO: small ubiquitin-related modifier, TEV: tobacco etch virus) preceding the N terminus of the target peptide was designed. Recombinant expression in E. coli and subsequent SUMO protease cleavage yielded the HisTag-TEV-target peptide. Partial protection of the lysine side chains of this peptide with d-glucopyranosyloxycarbonyl and removal of the HisTag-TEV sequence by TEV protease yielded the partially protected peptide with a free N-terminal amine. Coupling of selenocysteine selectively at the N terminus and subsequent acidic deprotection of the carbohydrate protecting groups yielded a modified peptide that can be used for native chemical ligation (NCL). As a proof of concept, the modification of a longer recombinant peptide with selenocysteinylserine (GalNAc) at the N terminus was demonstrated.

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The total synthesis of D-erythro-sphingosine (9) was performed by a chirospecific method starting from D-galactose via an azidosphingosine intermediate to give highly homogeneous ( > 99.9% C18:1) sphingosine base (9) which contained no observable olefin isomerization by product and was demonstrated to be optically pure by a novel method utilizing Mosher’s acid. Ceramide (10) was prepared from this sphingosine (9) with highly homogeneous (99.8% C16:0) palmitic acid by two methods. The cerebroside glucosylceramide (23) was the next sphingolipid in this series to be synthesized in a highly homogeneous form. These three sphingolipids are currently being used for biophysical studies of the structures of their hydrated bio-molecular assemblies.

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(Chemical Equation Presented) The first O-glycosylation of hydroxamic acids is reported. This process involves the use of glycosyl N-phenyl trifluoroacetimidates as glycosyl donors in the presence TMSOTf and 4 A molecular sieves in dichloromethane. Under such conditions, a wide range of new glycosyl donors including glucosyl, galactosyl, mannosyl, glucuronyl, and ribosyl hydroxamates were prepared in good to high yields. This procedure appears to be an advantageous alternative for the synthesis of glycosyl hydroxamates of biological interest.

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The chitin obtained from crustacean shell waste and other renewable resources may be used as a primary feedstock in the biorefineries of the future. Accordingly, the incorporation of chitin-derived building blocks into new synthesis processes will accentuate the utility of this biopolymer, particularly in the production of bio-based small molecules that contain one or more nitrogen atoms. Herein we report that enantioenriched 2-amino sugars are readily accessible from the chitin-derived platform 3-acetamido-5-acetylfuran (3A5AF). Subjecting 3A5AF to a Noyori reduction?Achmatowicz rearrangement sequence gave N-acetyl-l-rednose (RedNAc) in excellent yield and enantiopurity. Acetamide hydrolysis gave l-rednose, a rare 2-amino sugar found in natural anthracycline and angucycline antibiotics. RedNAc was subsequently shown to be a versatile platform from which a variety of stereochemically pure 2-amino sugars are readily attainable. The synthesis of chiral, bio-based N-compounds from chitin emphasises the rapidly expanding utility of this biopolymer as a viable platform for fine chemical production.

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O-acyl-protected glycosyl N-alkyl and N-phenyl carbamates are obtained with 100% diastereoselectivity from anomerically unprotected mono or disacacharides. Long-chain alkyl carbamates are surfactants. N-phenyl carbamates are good glycosyl donors.

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A method for determining the presence of mycobacteria species in an organism or biological sample, the method comprising adding to the organism or biological sample a probe molecule comprising a substrate and a label, which probe molecule can be incorporated into mycobacteria, the presence of mycobacteria being determined by a detector responsive to the presence of the label, optionally after applying a stimulus; suitable probe molecules include compounds comprising a label and a substrate, which label is can be detected by a detector responsive to the presence of the label, optionally after applying a stimulus, characterised by compound being able to engage with the active site of Antigen 85B (Ag85B) such that it can form simultaneous hydrogen bonds with two or more amino acids in the active site selected from Arg 43, Trp 264, Ser126, His 262 and Leu 42, or the corresponding amino acids in Antigen 85A (Ag85A) or Antigen 85C (Ag85C), at least one of which is with Ser126.

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The preparation of new glyco-organic substrates, along with their enhanced reactivity in water-promoted Claisen rearrangement, are described.The chirality induced by the glucose moiety during the course of the reaction is dependent upon the alpha- or beta-configuration of the anomeric centre.This allowed us to prepare enantiomerically pure (R) or (S) 1,3-diols 8, with D-glucose, as the unique source of chirality.

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As expected, the reactive acetyl-protected O-(alpha-D-glucopyranosyl) trichloroacetimidate 3 reacts with S-nucleophiles and trifluoroborane-ether as catalyst to yield exclusively 1-thio-beta-D-glucopyranosides with inversion of the configuration.The corresponding benzyl-protected alpha-trichloroacetimidate 4 affords with retention of the configuration alkyl 1-thio-alpha-D-glucopyranosides.The importance of alkyl 1-thio-beta-D-galactopyranosides in enzyme induction was reason to apply this convenient and efficient glycosyl-transfer reaction to the synthesis of isopropyl 1-thio-beta-D-galactopyranoside (12a) and the sodium salt of 1-thio-beta-D-galactopyranose (12b), respectively.

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We present the short synthesis of the suitably functionalized enantioselective dihydropyran core of secoiridoids using an N-heterocyclic carbene (NHC) catalyzed Coates-Claisen rearrangement mechanism. The key steps of the synthesis are (i) the highly enantioselective NHC catalyzed Coates-Claisen rearrangement for the dihydropyran core, (ii) the assembly of the target dihydropyran core structure of oleuropein from a highly diastereoselective exocyclic trans alkene, and (iii) the highly stereoselective assembly of a monoterpene elenolide core structure.

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Tetrahydropyran – Wikipedia,
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