Catalytic intermolecular Pauson-Khand-type reaction: strong directing effect of pyridylsilyl and pyrimidylsilyl groups and isolation of Ru complexes relevant to catalytic reaction

Some circumstantial evidence for the directing effect of the 2-pyridylsilyl group in the Ru-catalyzed intermolecular Pauson-Khand-type reaction (PKR) of alkenyl(2-pyridyl)silane, alkyne, and carbon monoxide has been provided. Most importantly, we have succeeded in isolating several monometallic Ru complexes relevant to the catalytic reaction: Ru(vinylsilane)(CO)(3) complexes and ruthenacyclopentene. While the stoichimetric reaction of the Ru(vinylsilane)(CO)(3) complex with an alkyne led to the formation of the corresponding cyclopentenone (PKR product) at 100 degrees C, the ruthenacyclopentene intermediate was quantitatively produced at 50 degrees C. This complex was also converted to a cyclopentenone upon heating at 100 degrees C. Moreover, it was also found that the Ru(vinylsilane)(CO)(3) complex and ruthenacyclopentene serve as catalysts in intermolecular PKR.     

A highly efficient asymmetric Suzuki-Miyaura coupling reaction catalyzed by cationic chiral palladium(ii) complexes

Cationic chiral palladium(ii) complexes are shown to catalyze the asymmetric coupling reaction of aryl boronates and aryl halides within a short period of time in good yield and enantioselectivity.     

30-mJ, diode-pumped, chirped-pulse Yb:YLF regenerative amplifier

A diode-pumped chirped-pulse regenerative amplifier with a cooled Yb:YLF crystal has been developed. The output pulse energy is 30 mJ at 20-Hz repetition rate. A high effective extraction efficiency of 68% is obtained, which is attributed to reduced saturation fluence at low temperature and to a high effective pulse energy fluence during regenerative amplification. After pulse compression by use of a parallel grating pair, 18-mJ pulse energy and 795-fs pulse duration are obtained.     

Lipase TL-mediated kinetic tesolution of 5-benzyloxy-1-tert-butyldimethylsilyloxy-2-pentanol at low temperature: concise asymmetric synthesis of both enantiomers of a piperazic acid derivative

Lipase TL-mediated kinetic resolution of (+/-)-5-benzyloxy-1-tert-butyldimethylsilyloxy-2-pentanol (5) at low temperature proceeded to give the corresponding (S)-alcohol 5 and (R)-acetate 6 in quantitative yields with high enantiomeric purity. The addition of bases such as pyridine, DMAP, 2,4- and 2,6-lutidines, or triethylamine considerably enhanced the rate of kinetic resolution. The alcohol (S)-5 and the acetate (R)-6 were converted to piperazic acid derivatives (R)- and (S)-3, respectively, via the intramolecular Mitsunobu reaction as a key step.     

Studies on the constituents of Gardenia species. III. New iridoid glycosides from the leaves of Gardenia jasminoides cv. fortuneana Hara

Two new iridoid glycosides, 7 beta,8 beta-epoxy-8 alpha-dihydrogeniposide (1) and 8-epiapodantheroside (2), were isolated, together with six known (3-8) and three artifact (9-11) iridoids, from the leaves of Gardenia jasminoides cv. fortuneana Hara. Their structures were established based on chemical and spectral data.     

Functional Fluorescence Labeling of Carbohydrates and Its Use for Preparation of Neoglycoconjugates

Abstract

New bifunctional reagents, 2-amino-6-carboxyethylpyridine and 2-amino-6-cyanoethylpyridine, were designed and synthesized in order to provide a novel procedure for preparation of neoglycoconjugates from fluorescence-labeled and purified sugar chains. Labeling of model sugar chains with these reagents was effected by reductive amination using BH₃.Me₂NH to give corresponding 6-carboxyethylpyridylaminated (CEPA-) and 6-cyanoethylpyridylaminated (CNEPA-) derivatives, which were readily purified by reversed phase HPLC. The reagent parts of the labeled products possess the functional groups which then serve as linkers for coupling with matrices such as proteins and polymers. A CEPA-derivative of glucose was directly coupled with the ε-amino group of a Lys derivative to give a neoglycoprotein model. CNEPA-sugars were hydrogenated to give 6-aminopropylpyridylaminated (APPA-) derivatives, which can then be readily used for the preparation of various types of neoglycoconjugates by use of appropriate spacers as exemplified by the coupling of APPA-maltotriose with bovine serum albumin (BSA), biotin, and acrylic acid. The reaction of APPA-maltotriose with succinimidyl 3-(3-nitro-2-pyridyldithio)propionate gave the corresponding amide to be used for a disulfide formation with BSA. Condensation with biotin was effected by use of N-hydroxysuccinimidobiotin. The conjugation of APPA-maltotriose with acrylic acid was carried out by use of 4-acryloyloxyphenyldimethylsulfonium methylsulfate to give the corresponding acrylamide, which can be used for the preparation of sugar-acrylamide copolymers.     

‘Calixarene-like’ chiral amine macrocycles as novel chiral shift reagents for carboxylic acids

Chiral macrocyclic amine 2 was found to be useful as an NMR chiral shift reagent for the determination of the enantiomeric purity and absolute configurations of several kinds of carboxylic acid and amino acid derivatives.     

Oxidation of Dimethyl Sulfide in Air Using Electron-Beam Irradiation,and Enhancement of its Oxidation Via an MnO<Subscript>2</Subscript> Catalyst

The decomposition of dimethyl sulfide (DMS) at initial concentrations of 4.5–18.0 ppmv in air was studied under electron-beam (EB) irradiation. Doses to decompose 90% of input DMS were 2.5 kGy for 4.5 ppmv, 3.4 kGy for 10.6 ppmv, and 3.9 kGy for 18.0 ppmv. HCOOH, (CH₃)₂SO, and trace CH₃OH and (CH₃)₂SO₂ were produced as irradiation products in addition to CO₂ and CO. Application of an O₃ decomposition catalyst to an irradiated sample gas led to an enhancement in the oxidation of DMS and its products into CO₂ and the decomposition of O₃. For 10.6 ppmv DMS/air, the mineralization ratio increased from 41% via only EB irradiation to 100% via the combination treatment at 6.3 kGy. The yield of CO₂ to CO_x increased from 5.3 to 87.6% by combination with catalytic oxidation. This combination treatment enables the irradiation energy used to deodorize gas streams containing DMS to be reduced.     

Dimethylarsinic acid targets tubulin in mitotic cells to induce abnormal spindles

Dimethylarsinic acid (DMA) is the most effective inducer of cell‐cycle disruption among the arsenic compounds and their metabolites. The present study was conducted to gain further insight into cell‐cycle disruption induced by DMA. The inhibition of cell proliferation and the mitotic arrest induced by DMA were significant and dose‐dependent in Chinese hamster V79 cells and the two seemed to be closely related. At less than 140 µM the DMA did not inhibit the proliferation of cells, but it significantly induced mitotic arrest. An indirect immunofluorescence assay using anti‐α‐tubulin antibodies revealed that DMA induced the formation of abnormal spindles in the metaphase cells even at 350 µM with 5 h of treatment. At 1.4 mM DMA no metaphase cells could form a definite spindle structure. The spindle figures were similar to those induced by colchicine (125 nM ) or vinblastine (110 nM ), major antimitotic agents. In DMA‐treated interphase cells, the microtubule networks were indistinguishable from those of normal cells. With the tubulin‐assembly assay estimated by turbidity, DMA at less than 200 µM suppressed tubulin assembly in a dose‐dependent manner, whereas at more than 700 µM it enhanced tubulin polymerization remarkably with or without addition of excess guanosine‐5′‐triphosphate. According to the above findings, we discussed the possibility that DMA, a primary metabolite of inorganic arsenic in mammals, is related to arsenic carcinogenicity. Copyright © 2001 John Wiley & Sons, Ltd.     

Macroporous Morphology of the Titania Films Prepared by a Sol-Gel Dip-Coating Method from the System Containing Poly(Ethylene Glycol). III. Effect of Chemical Additives

The variation of macroporous morphology has been studied for the titania (TIO₂) films prepared by a sol-gel dip-coating method from the system containing poly(ethylene glycol) (PEG) under the addition of various types of organic solvents. The influence of externally-added solvent is interpreted by considering the compatibility between PEG and the solvent mixture, the volatility of the solvent mixture, and the polycondensation rate of titania oligomers. The macroscopic domain formation is remarkable when the compatibility between the solvent mixture and PEG is relatively poor and the boiling point of external solvent is relatively low.