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The development of gamma-thionorleucine (ThioNle) as a handle for native chemical ligation-desulfurization is reported here. ThioNle is a new addition to the expanding thiolated amino acid toolbox and serves as a methionine substitute in NCL with the advantage that it lacks the undesirable oxidation-prone thioether moiety. Its usefulness for N-terminal ubiquitination is demonstrated by efficient preparation of fully synthetic linear diubiquitin with preserved protein folding compared to the expressed material. Interestingly, gel-based deubiquitinating assays revealed that the methionine to norleucine substitution did affect diubiquitin cleavage, which may indicate a more profound role for methionine in the interaction between ubiquitin and the deubiquitinating enzymes than has been known so far.

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Both enantiomers of 3-deoxysphingosine as well as their cis-isomers were synthesized stereoselectively from L- and D-serine.

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Enantiomerically pure nor-furanomycin, furanylglycine, furanylalanine and homo-furanylalanine derivatives were prepared from appropriate amino acid derived dienes using ring-closing metathesis as the key step. Georg Thieme Verlag Stuttgart.

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A new protocol based on a palladium-catalyzed Heck reaction of an amino acid-derived vinyl unit with 3-bromoquinoline has been developed to access the title compounds in good yield and optical purity. Copyright

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The enzymatic resolution of the N-phenylacetyl derivative of racemic homoserine lactone with penicillin G acylase immobilized on Eupergit C gave (R)-(+)-alpha-amino-gamma-butyrolactone and (S)-(-)-alpha-N- phenylacetamido-gamma-butyrolactone in high enantiomeric purity (ee >99%) and 46-47% yields for each enantiomer. The enantiomers were converted into azasugars 1,4-dideoxyallonojirimycin and 1,4-dideoxymannojirimycin using Wittig olefination, catalytic ring-closing metathesis (RCM), and stereoselective dihydroxylation with OsO4 in 29% overall yield over 11 high yielding steps. Enzyme inhibition studies showed that 1,4-dideoxyallonojirimycin is a better beta-glucosidase inhibitor (IC50 32.4 muM toward beta-glucosidase from almonds) and a better beta-galactosidase inhibitor (IC50 5.9 mM for beta-galactosidase from Aspergillus oryzae) than 1,4-dideoxymannojirimycin (IC50 2.86 mM and 12.5 mM for beta-glucosidase and beta-galactosidase, respectively).

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Chemical engineers ensure the efficiency and safety of chemical processes, adapt the chemical make-up of products to meet environmental or economic needs, and apply new technologies to improve existing processes. Computed Properties of C12H21NO4. Introducing a new discovery about 147959-19-1, Name is (S)-tert-Butyl 2,2-dimethyl-4-(2-oxoethyl)oxazolidine-3-carboxylate

A general access to a novel class of sugar alpha-amino acids composed of iminofuranose and iminopyranose residues anomerically linked to the glycinyl group through an alkyl chain is described. A set of eight compounds was prepared by the same reaction sequence involving as an initial step the Grubbs Ru-carbene-catalyzed cross-metathesis (CM) of various N-Cbz-protected allyl C-iminoglycosides with N-Boc-vinyl- and N-Boc-allyloxazolidine. The isolated yields of the CM products (mixtures of E- and Z-alkenes) varied in the range 40-70%. Each mixture was elaborated by first reducing the carbon-carbon double bond using in situ generated diimide and then unveiling theTV-Boc glycinyl group [CH(BOcNH)CO2H] by oxidative cleavage of the oxazolidine ring by the Jones reagent. All amino acids were characterized as their methyl esters. The insertion of a model C-iminoglycosyl-2-aminopentanoic acid into a tripeptide via sequential carboxylic and amino group coupling with L-phenylalanine derivatives was carried out as a demonstration of the potential of these sugar amino acids in designed glycopeptide synthesis.

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The synthetic utility of proline-catalyzed asymmetric alpha-hydroxylation and subsequent reductive amination of aldehydes to afford chiral beta-amino alcohols is explored for the first time. Stereoselective synthesis of orthogonally protected 5-hydroxylysine, 4-hydroxyornithine and 2,4-diamino-3-hydroxybutanoic acid was achieved. (2S,5S)-5-Hydroxylysine synthesized in this way was converted into the aminocaprolactam ring system of bengamide A.

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A diastereoselective route to the synthesis of D-threo-sphinganine, L-erythro-sphinganine and (?)-spisulosine from the higher homologue of Garner’s aldehyde prepared from L-aspartic acid is reported. While the starting material contains one of the stereocenters in the target molecules, the other is generated by proline-catalyzed asymmetric alpha-hydroxylation of the aldehyde function. The two diastereomers of sphinganine are prepared from the same starting material and using the same sequence of reactions, but for the proline isomer used as the catalyst. The method described is simple and efficient and can easily be extended for the synthesis of other sphingoid bases.

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Bacterial cell wall peptidoglycan (PGN) is a potent immunostimulator and immune adjuvant. The PGN of Gram-negative bacteria and some Gram-positive bacteria contain meso-diaminopimelic acid (meso-DAP), and we have recently shown that the intracellular protein Nodi is a PGN receptor and recognizes DAPcontaining peptides. In this study, we achieved the synthesis of DAP-containing PGN fragments, including the first chemical synthesis of tracheal cytotoxin (TCT), GlcNAc-(beta1-4)-(anhydro) Mur-NAc-L-Ala-gamma-D-Glu-meso- DAP-D-Ala, and a repeating-unit of DAP-type PGN, GlcNAc-(beta1-4)-MurNAc-L- Ala-gamma-D-Glu-meso-DAP-D-Ala. For the synthesis of PGN fragments, we first established a new synthetic method for an orthogonally protected meso-DAP derivative, and then we constructed the glycopeptide structures. The ability of these fragments to stimulate human Nodi, as well as differences in Nodi recognition of the variety of synthesized ligand structures were examined. The results showed that the substitution of the N terminus of iE-DAP is necessary for stronger Nodi recognition, but the structure of the substituent seems not to be strictly recognized. The importance of the carboxyl group at the 2-position of DAP for human Nod1 stimulation was also shown.

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There are provided novel compounds of formula (I) wherein T, X, Y and W are as defined in the specification, and pharmaceutically acceptable salts thereof, and enantiomers and racemates thereof; together with processes for their preparation, compositions containing them and their use in therapy. The compounds arc inhibitors of nitric oxide synthase and are thereby particularly useful in the treatment or prophylaxis of inflammatory disease and pain.

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