First total synthesis of antitumor natural product (+)- and (-)-pericosine A: determination of absolute stereo structure

The first total synthesis of (+)- and (-)-pericosine A has been achieved, enabling the revision and determination of the absolute configuration of this antitumor natural product as methyl (3S,4S,5S,6S)-6-chloro-3,4,5-trihydroxy-1-cyclohexene-1-carboxylate. Every step of this total synthesis proceeded well with excellent stereoselectivity. Structures of the intermediates in crucial steps were confirmed by detailed 2D NMR analysis.     

Highly efficient synthesis of optically pure 5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol and -naphthylamine derivatives by partial hydrogenation of 1,1'-binaphthyls with carbon nanofiber supported ruthenium nanoparticles

Use of Ru/CNF-P, nanoruthenium particles dispersed on a nanocarbon fiber support, realizes highly efficient catalytic partial hydrogenation of 1,1'-bi-2-naphthol and -naphthyl-amine derivatives. The reactions proceed in high turnover numbers without racemization of the axial chirality, offering a practical procedure for the production of optically pure 5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyls in good to high yields.     

Rubusuaviins A-F, monomeric and oligomeric ellagitannins from Chinese sweet tea and their alpha-amylase inhibitory activity

Six new ellagitannins herein, rubusuaviins A-F, were isolated from the aqueous acetone extract of Chinese sweet tea (Tien-cha, dried leaves of Rubus suavissimus S. LEE) together with seven known tannins. Rubusuaviin A was characterized as 1-O-galloyl-2,3-O-(S)-HHDP-4,6-O-(S)-sanguisorboyl-beta-D-glucopyranose. Rubusuaviins B, C, and E are dimeric, trimeric, and tetrameric ellagitannins, respectively, in which the sanguisorboyl groups were connected ellagitannin units. Rubusuaviins D and F were desgalloyl derivatives of rubusuaviins C and E, respectively. The inhibition of alpha-amylase activity by rubusuaviins and related ellagitannins was compared. Ellagitannins with beta-galloyl groups at the glucose C-1 positions showed stronger inhibition compared with the alpha-galloyl and desgalloyl compounds. The molecular weight of these compounds was not important for the inhibition of alpha-amylase activity.     

Novel 2-mercaptopyridine-ruthenium complex exhibiting electrochemically induced linkage isomerization switched on/off by protolysis

A ruthenium complex [ruthenium bis(2,2'-bipyridine)(2-mercaptopyridine)(pyridine)](PF6)2 was crystallographically characterized from its deprotonated form and was electrochemically investigated. In the deprotonated complex, the 2-mercaptopyridine ligand coordinates to the Ru atom only by the S atom; therefore, the N atom of the 2-mercaptopyridine ligand can be protonated. In a CH3CN solution, the complex shows a reversible redox couple attributed to RuIII/II-S. The addition of a base to the CH3CN solution of the complex gives irreversible voltammograms, implying electrochemically induced linkage isomerization between RuII-S and RuIII-N. Analysis of the observed cyclic voltammograms gave the equilibrium and rate constants for linkage isomerization: KIINS = 1.2 x 1018, KIIINS = 0.64, kIINS = 5 x 10 s(-1), kIISN = 4 x 10-17 s(-1), kIIINS = 0.26 s(-1), and kIIISN = 0.40 s(-1).     

Redox silencing of the Fenton reaction system by an alkylitaconic acid, ceriporic acid B produced by a selective lignin-degrading fungus, Ceriporiopsis subvermispora

The selective lignin-degrading fungus, Ceriporiopsis subvermispora secretes alkylitaconic acids (ceriporic acids) during wood decay. We reported that ceriporic acid B (hexadecylitaconic acid) was protective against the depolymerization of cellulose by the Fenton reaction. To understand the redox silencing effects, we analyzed the physicochemical and redox properties of itaconic, octylitaconic and hexadecylitaconic acids. The initial rate of HO production by the Fenton system with Fe(3+), H(2)O(2) and L-cysteine was suppressed by hexadecylitaconic and octylitaconic acids by 0.04 and 0.16 of the reaction rate without chelators. ESR, O(2) uptake and the assay of Fe(2+) with BPS demonstrated that Fe(3+) reduction by L-cysteine was suppressed by hexadecylitaconic and octylitaconic acids while the reaction of Fe(2+) with H(2)O(2) was not suppressed by the two alkylitaconic acids. Ligand exchange experiments with NTA demonstrated that Fe(3+) chelation by two carboxyl groups of alkylitaconic acids is a critical step in iron redox modulation. In stark contrast, the production of HO* and reduction of Fe(3+) were not suppressed by itaconic acid due to HO*--initiated degradation of the chelator. The strong redox silencing effects by a series of alkylitaconic acids have attracted interest in controlling microbial plant cell wall degradation and chemoprotection against cellular oxidative injury.     

Facile synthesis of amine-terminated aromatic polyamide dendrimers via a divergent method

[structure: see text]. A novel, rapid, inexpensive, and highly efficient divergent approach for the synthesis of a 32-amine-terminated G4 polyamide dendrimer has been developed. Each generation dendrimer was successfully obtained by the condensation of the preceding generation dendrimer with the building block and the deprotection with hydrazine in one pot. All the dendrimers were easily purified by precipitation in alkaline water, and the purity was confirmed by NMR, MALDI-TOF mass spectra, and elemental analysis.     

Fast preparation of PtRu catalysts supported on carbon nanofibers by the microwave-polyol method and their application to fuel cells

PtRu alloy nanoparticles (24 +/- 1 wt %, Ru/Pt atomic ratios = 0.91-0.97) supported on carbon nanofibers (CNFs) were prepared within a few minutes by using a microwave-polyol method. Three types of CNFs with very different surface structures, such as platelet, herringbone, and tubular ones, were used as new carbon supports. The dependence of particles sizes and electrochemical properties on the structures of CNFs was examined. It was found that the methanol fuel cell activities of PtRu/CNF catalysts were in the order of platelet > tubular > herringbone. The methanol fuel cell activities of PtRu/CNFs measured at 60 degrees C were 1.7-3.0 times higher than that of a standard PtRu (29 wt %, Ru/Pt atomic ratio = 0.92) catalyst loaded on carbon black (Vulcan XC72R) support. The best electrocatalytic activity was obtained for the platelet CNF, which is characterized by its edge surface and high graphitization degree.     

Infrared spectroscopic investigation of poly(2-methoxyethyl vinyl ether) during thermosensitive phase separation in water

Hydration changes of poly(2-methoxyethyl vinyl ether) (PMOVE) synthesized via living cationic polymerization have been investigated during a temperature-responsive phase separation in water by using infrared spectroscopy. An aqueous PMOVE solution has lower critical solution temperatures (LCSTs) of 66 degrees C in H2O and 65 degrees C in D2O at approximately 15 wt %. During phase separation, the C-H stretching (nu(C-H)) bands of PMOVE shift downward (red shift). In particular, the IR band assigned to the antisymmetric stretching vibration of the terminal methyl groups exhibits a remarkably large red shift by 16 cm-1. The band also exhibits a red shift with increasing polymer concentration at T < Tp. Density functional theory (DFT) calculations of the models of hydrated PMOVE indicate that the shift is due mainly to the breaking of hydrogen bonds (H-bonds) between the oxygen of the methoxy groups and water and partially to the breaking of the CH...O H-bond to them.     

Building Block approach to SiO2–ZrO2 porous materials†

(2‐Hydroxyethyl)trimethylammonium silicate, Si₈O₂₀[N(CH₃)₃(C₂H₄OH)]₈·nH₂O, was allowed to react with zirconium tetrakis(2,4‐pentanedionate) in methanol, resulting in gel formation. The gels were heat‐treated at 650–1000 °C in air. The product at 650 °C showed a specific surface area of 500 m² g⁻¹, and the average pore diameter was ca 4.3 nm, indicating the formation of a thermally stable mesoporous body. Gels with the same composition were also prepared by sol–gel processing using tetraethoxysilane as a silica source. The specific surface area of the product yielded by heating the gels at 650 °C was 425 m² g⁻¹ and the average pore diameter was ca 2.8 nm, which were lower than those of the product from the gels prepared with (2‐hydroxyethyl)trimethylammonium silicate. These differences have been attributed to the difference in nanostructure of the gels, caused by the structure of the silica sources and their polymerization behaviour. Copyright © 1999 John Wiley & Sons, Ltd.     

Synthetic Design of Carbonyl‐Group‐Containing Compounds Based on C−O Bond Cleavage Promoted by Pd Complexes

On the basis of fundamental studies on elementary processes involving allyl−O and acyl−O bond cleavages, various new catalytic processes to convert carboxylic acid derivatives have been realized. The new processes include 1) carbonylation of allyl formates to β,γ‐unsaturated acids, 2) amination, alkylation, and carbonylation of allylic alcohols, 3) aldehyde synthesis by hydrogenation of carboxylic anhydrides and carboxylic acids, 4) ketone synthesis by combination of the C−O bond cleavage with transmetallation by organoboronic acids. The processes described here have advantages over the conventional ones in that they are more atom‐efficient and halogen‐free in realizing the syntheses of a variety of carbonyl‐containing compounds under mild conditions.