Simple synthesis of beta-D-glycopyranosides using beta-glycosidase from almonds

Enzymatic glycosidation of twenty-one kinds of alcohols (n-hepanol, n-octanol, 2-phenylethanol, 3-phenylpropanol, 4-phenylbutanol, 5-phenylpentanol, 6-phenylhexanol, furfury alcohol, 2-pyridinemethanol, isobutanol, isopentanol, p-methoxycinnamylalcohol) including secondary alcohols (isopropanol, cyclohexanol, 1-phenylethanol) and 1,omega-alkanediols (1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol), salicyl alcohol and 4-nitrophenyl beta-D-glucopyranoside (5) using beta-glucosidase from almonds stereoselectively gave the corresponding beta-D-glucopyranosides in moderate yield.     

Synthesis of methyl 1-O-(4-hydroxymethamphetaminyl)-alpha-D-glucopyranouronate

For the purpose of the direct characterization of the intact conjugated form in the urine of a methamphetamine (MA) abuser, 4-hydroxymethamphetamine (4-OHMA) glucuronate, corresponding to one of the metabolites of MA, was synthesized from the commercially available methyl 4-hydroxyphenylacetate.     

Some reactions of mono substituted pyrazine monoxides

The reactions of the monoxides of propylpyrazine and phenylpyrazine with phosphoryl chloride or acetic anhydride were investigated. Except in the case of the reaction of 2-propylpyrazine 1-oxide with acetic anhydride, chlorination or acetoxylation occurred on the pyrazine ring in all cases; moreover, these reactions occurred preferentially at the position poorest in π-electron density. The N-oxidation and the successive chlorination of monochloro-phenylpyrazines were also investigated, and the structures of the products were confirmed.     

13C NMR spectra of alkyl- and phenylpyrazines and their N-oxides

The ¹³C chemical shifts of 37 pyrazines, including their N-oxides, are reported. Substituent effects of methyl, phenyl and N-oxide groups on the chemical shifts were examined. To comprehend these effects, the chemical shifts were compared with charge densities calculated by the CNDO/2 method and a good correlation was obtained. ¹³C, ¹H coupling constants of some pyrazines were also determined and assigned. These data enable us to assign the ¹³C NMR spectra of substituted pyrazines and to understand the effects of N-oxidation on the pyrazine nuclei.     

Solution synthesis of human neuropeptide Y (hNPY)

Human neuropeptide Y (hNPY) was synthesized in a conventional manner by assembling seven peptide fragments followed by reduction of the Met(O) residue with phenylthiotrimethylsilane and subsequent deprotection with 1 M trimethylsilyl trifluoromethanesulfonate (TMSOTf)-thioanisole in trifluoroacetic acid (TFA). Alternatively, deprotection was performed in a two-step manner; first, treatment with 1 M trimethylsilyl bromide-thioanisole in TFA, and then with 1 M TMSOTf-thioanisole in TFA. After purification by gel-filtration on Sephadex G-25, followed by reversed-phase high-performance liquid chromatography, a highly purified sample of synthetic hNPY was obtained in both cases. When administered in dogs, synthetic hNPY was as active as porcine NPY in terms of the effects on systemic arterial blood pressure, pancreatic blood flow, and superior mesentric artery (SMA) blood flow. Met(O)17-hNPY was found to be as active as the parent sample in these bioassays.     

Solvolysis of (4,5)-anti-4-aryl-5-tosyloxy-2(E)-hexenoate derivatives

The solvolysis reaction of (4,5)-anti-4-aryl-5-tosyloxy-2(E)-hexenoates 4a-k gave (4,5)-anti-4-aryl-5-hydroxy-2(E)-hexenoates 2a-k and (4,5)-anti-5-aryl-4-hydroxy-2(E)-hexenoates 5a-k along with the complete inversion. This 1,2-aryl migration was induced by treatment with heating in water-saturated nitromethane. On the basis of the substituent effect on the aromatic ring, this 1,2-aryl migration is thought to proceed via the sigma-bridged phenonium ion. The product selectivity between 2a-k and 5a-k was found to be subtly governed by the substituent and substitution pattern in the aromatic ring of the substrates 4a-k.