Two novel aromatic glycosides,pueroside-A and -B,from puerariae radix

Two novel aromatic glycosides were obtained from Puerariae Radix and their chemical structures were characterized.     

Aurilide, a cytotoxic depsipeptide from the sea hare Dolabella auricularia: isolation, structure determination, synthesis, and biological activity

The bioassay-guided fractionation of the cytotoxic constituents of the Japanese sea hare Dollabella auricularia led to the isolation of aurilide (1), a 26-membered cyclodepsipeptide. The gross structure of 1 was established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure was determined by chiral HPLC analysis of acid hydrolysates of 1 and by the enantioselective synthesis of a degradation product arising from a dihydroxylated fatty acid portion. The enantioselective synthesis of 1 was achieved in 12% overall yield (16 steps) and confirmed the absolute stereostructure of 1. The cytotoxicity of 1 was evaluated using a synthetic sample, which was found to exhibit potent cytotoxicity against HeLa S₃ cells with an IC₅₀ of 0.011 μg/mL. Further biological and pharmacological studies of 1 have been carried out by using synthetic 1.     

Ru(II)-catalyzed chemo- and regioselective cyclotrimerization of three unsymmetrical alkynes through boron temporary tether. One-pot four-component coupling via cyclotrimerization/Suzuki-Miyaura coupling

The Ru(II)-catalyzed [2+2+2] cyclotrimerization of alkynylboronates, propargyl alcohol, and terminal alkynes proceeded chemo- and regioselectively to give rise to arylboronates, which were subjected to Suzuki-Miyaura cross-coupling with aryliodides to afford highly substituted biaryls in 53-76% yields.     

First radical cation salts of 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions: β-(BDA-TTP)4Cu2Cl6 and (BDA-TTP)2CuCl4

New radical cation salts based on 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions, β-(BDA-TTP)₄Cu₂Cl₆ and (BDA-TTP)₂CuCl₄, were synthesized and structurally characterized. Single crystals were prepared by electrochemical oxidation of BDA-TTP under galvanostatic conditions. X-ray diffraction study demonstrated that the salts have a layered structure, in which the conducting BDA-TTP layers alternate with the [Cu₂Cl₆]²⁻ or [CuCl₄]²⁻ anions. Both salts show the semiconductor-type temperature dependence of the conductivity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–54, January, 2007.     

Combinatorial synthesis of MUC1 glycopeptides: polymer blotting facilitates chemical and enzymatic synthesis of highly complicated mucin glycopeptides

The chemoselective polymer blotting method allows for rapid and efficient synthesis of glycopeptides based on a "catch and release" strategy between solid-phase and water-soluble polymer supports. We have developed a heterobifunctional linker sensitive to glutamic acid specific protease (BLase). The general procedure consists of five steps, namely (i) the solid-phase synthesis of glycopeptide containing BLase sensitive linker, (ii) subsequent deprotections and the release of the glycopeptide from the resin, (iii) chemoselective blotting of the glycopeptide intermediates in the presence of water-soluble polymers with oxylamino functional groups, (iv) sugar elongations using glycosyltransferases, and (v) the release of target glycopeptides from the polymer platform by selective BLase promoted hydrolysis. The combined use of the solid-phase chemical syntheses of peptides and the enzymatic syntheses of carbohydrates on water-soluble polymers would greatly contribute to the production of complicated glycopeptide libraries, thereby enhancing applicative research. We report here a high-throughput synthetic system for the various types of MUC1 glycopeptides exhibiting a variety of sugar moieties. It is our belief that this concept will become part of the entrenched repertoire for the synthesis of biologically important glycopeptides on the basis of glycosyltransferase reactions in automated and combinatorial syntheses.     

A novel synthesis of (+)-biotin from L-cysteine

(+)-Biotin (1) was synthesized in 25% overall yield over 11 steps from L-cysteine. The contiguous asymmetric centers at C-3a and C-6a were formed through a novel and highly stereoselective Lewis base-catalyzed cyanosilylation of alpha-amino aldehyde 3 to provide anti-O-TMS-cyanohydrin 4 with high stereoselectivity and in high yield (anti/syn = 92:8, 96%). Treatment of 4 with a di-Grignard reagent, 1,4-bis(bromomagnesio)butane, followed by carbon dioxide, efficiently installed the 4-carboxybutyl chain at C-4 to give keto acid 5. The final cyclization to bicyclic compound 7b, a precursor to 1, was realized by a palladium-catalyzed intramolecular allylic amination of cis-allylic carbonate 6b that was elaborated from 5.     

Evaluation of thallium-201 myocardial emission computed tomography based on a comparison with postmortem findings

The correlative study of myocardial perfusion assessed by 201Tl myocardial ECT with the pathological finding of the heart was performed in 10 autopsied cases with mean age of 77 years old (range: 60-90 y). In 6 cases with myocardial infarction (MI) 7 perfusion defects were observed, that was, 3 in anteroseptal wall, 1 in anterolateral wall and 3 in posterior wall on the images of SPECT. Seven MIs were also found in postmortem examination. Six MIs were observed at autopsy corresponding to perfusion defect on SPECT images. In one myocardial perfusion defect at inferoposterior portion on SPECT, a non-transmural MI was found at anteroseptum. In one case with valvular disease a false positive result was obtained at posterior wall where neither myocardial necrosis nor fibrosis was observed at autopsy. This case had aortic stenosis due to bicuspid aortic valve by autopsy. The ventricle was divided into 16 segments in each of 4 short axial images to evaluate extent of MI. SPECT for extent of MI showed sensitivity of 81.9%, specificity of 96.0% and diagnostic accuracy of 92.5%. False negative segment was apt to be observed at the surrounding of non-transmural MI or basal half of left ventricle (LV) with transmural MI, while false positive segment was at posterior portion of basal half of LV. It was concluded that myocardial ECT was useful for evaluation of the site and extent of MI.     

Molecular orbital calculation of Mössbauer parameters for Sn(CH3)nH4−n (n=0, 1, 2, 3) and their photoproducts in low temperature matrices

Mössbauer parameters of tin compounds, Sn(CH₃)₂H_4–n (n=0, 1, 2, 3, 4), isolated in low temperature matrices were related to electronic properties at the tin nuclei obtained by molecular orbital calculations. Structures of novel species, Sn(CH₃)₂ and Sn(CH₃)H, produced via photodissociation of matrix-isolated Sn(CH₃)₃H and Sn(CH₃)₂H₂, respectively, were determined on the basis of molecular orbital calculations as compared with Mössbauer parameters. The correlations between Mössbauer quadrupole splitting and calculated electric field gradient using STO-3G or MINI-4 were found to depend on the valence of tin atoms because of poor allowance for basis sets in describing highly polar molecules.     

A study of hepato-biliary and alimentary scintigrams using a triple tracer method

In order to evaluate the gastric emptying and postprandial mixing of bile with food, the scintigraphies of hepatobiliary and gastrointestinal tracts by using three different kinds of radioisotopes were performed simultaneously (99mTc-E.HIDA for hepatobiliary scintigraphy, 111In-DTPA containing orange juice and 131I-albumin containing scrambled egg for gastrointestinal scintigraphy). This method was available for observation of gastric emptying of liquid and solid foods and also examination of the mixing effect of bile and food quantitatively.