Syntheses of (5E)-PGE2 and New 6-Functionalized Derivatives by the Use of Palladium-Catalyzed Decarboxylative Allylic Alkylation

(5 )-Prostaglandin E₂ (7) was synthesized fron ( )-4- -butyldimethylsilyloxy-2-cyclopentenone (1) by 2-alkenyloxycarbonylatlon of the organocopper conjugate-addition adduct (3) followed by intramolecular palladium-catalyzed decarboxylative allylic alkylation. The (5 )-prostaglandin E₂ skeleton was also obtained from the β-keto allylic ester (11) by a similar decarboxylative allylic alkylation. The decarboxylative allylic alkylation of another type of the three-component coupling product (12) gave new 6-methyleneprostaglandin E1 skeleton (15a), which was converted into new 6-methylprosta-glandin I methyl ester (20) 6-methyleneprostaglandin F₁ derivative (16) by two different ways. The stereochemistry of this intramolecular decarboxylative allylic alkylation was discussed in the reaction of 2-[( )- or ( )-2-butenyloxy-carbonyl] cyclopentanone systems.     

Energy-scale dependence of the lepton flavor-mixing matrix

We study an energy-scale dependence of the lepton flavor-mixing matrix in the minimal supersymmetric standard model with the effective dimension-five operators, which give Majorana masses of neutrinos. We analyze the renormalization group equations of the coefficients () of these effective operators under an approximation that neglects terms of order . We find that only (where is the generation number) real independent parameters in the lepton flavor-mixing matrix depend on the energy scale. In particular, all the phases in are scale-independent. Received: 10 April 1999 / Revised version: 23 May 1999 / Published online: 28 September 1999     

Self-association of water-soluble fluorinated diblock copolymers in solutions

The self-association of the fluorinated diblock copolymer, poly(methacrylic acid)-block-poly(perfluorooctylethyl methacrylate) (PMAA-b-PFMA), in water has been investigated by light scattering, potentiometry, atomic force microscopy, and transmission electron microscopy. The size of the polymer micelles increases, as the degree of dissociation of the PMAA blocks increases. Since the charged PMAA block takes the stretched structure, PMAA-b-PFMA can easily form large micelles due to the low steric hindrance of PMAA blocks. Addition of NaCl shielded electrostatic repulsion in the PMAA chain and induced the formation of smaller micelles than water without NaCl did because of the bulky structure of the PMAA chain in the shell of the micelles. The micelle of PMAA-b-PFMA in ethanol is larger than that of poly(t-butyl methacrylate)-block-poly(perfluorooctylethyl methacrylate) (PtBMA-b-PFMA) in ethanol as a result of the higher steric hindrance of the PtBMA block. The dimensions of the core and shell of the micelles were estimated. The micelle of PMAA-b-PFMA in water possesses a rather thick shell and a large volume per molecule, consistent with the extended PMAA chain. On the other hand, the shell of the micelle in an ethanol solution of PtBMA-b-PFMA is thin but has a large surface area. Facts are consistent with the shrunk structure of the PtBMA block in poor solvent.     

Morphology and mechanical properties of ultra-high molecular weight polyethylene-poly(tetrafluoroethylene) blend films

This paper deals with the morphology and mechanical properties of blend films for polytetrafluoroethylene (PTFE) and ultra-high molecular weight polyethylene (UHMWPE) prepared by kneading techniques. This experiment was carried out for blend films, prepared with different compositions of PTFE and UHMWPE to improve thermal properties of PE. In spite of the incompatibility of the two polymers, the blend film with the PTFE/UHMWPE composition =75/25 was maintained under the measurement of complex modulus at temperature higher than 300°C. This indicates that the UHMWPE chains dispersed in PTFE fibrous texture were not separated by the melting flow of UHMWPE at 300°C. To check the origin of this interesting phenomenon, the morphology of the blend films was investigated by using scanning electron microscopy, X-ray diffraction, and¹³C nuclear magnetic resonance.     

Catalytic,asymmetric Mannich-type reactions of N-acylimino esters: reactivity,diastereo- and enantioselectivity,and application to synthesis of N-acylated amino acid derivatives

In the presence of a catalytic amount of Cu(OTf)(2)-chiral diamine 3e complex, N-acylimino esters reacted with silyl enol ethers to afford the corresponding Mannich-type adducts in high yields with high enantioselectivities. A wide variety of silyl enol ethers derived from ketones, as well as esters and thioesters, reacted smoothly. In the reactions of alpha-substituted silyl enol ethers (alpha-methyl or benzyloxy), the desired syn-adducts were obtained in high yields with high diastereo- and enantioselectivities. Several intermediates for the synthesis of biologically important compounds were prepared using this novel catalytic asymmetric Mannich-type reaction, and at the same time, absolute and relative stereochemical assignments were made. In addition, it has been revealed that alkyl vinyl ethers reacted with N-acylimino esters in the presence of a catalytic amount of the Cu(II) catalyst to give the corresponding Mannich-type adducts in high yields with high enantioselectivities. This is the first example of catalytic asymmetric Mannich-type reactions with alkyl vinyl ethers. The reaction mechanism, structure of chiral catalyst-electrophile complexes, and transition states of these catalytic asymmetric reactions were assumed based on X-ray crystallographic analysis of the Cu(II)-chiral amine complex, PM3 calculations, and FT-IR analyses, etc. Finally, (1R,3R)-N-(3-hydroxy-1-hydroxymethyl-3-phenylpropyl)dodecanamide (HPA-12, 1), a new inhibitor of ceramide trafficking from endoplasmic reticulum to the site of sphingomyerin (SM) synthesis, has been synthesized efficiently using the present Mannich-type reaction as a key step. The synthesis involved three steps (two-pot), and total yield was 82.9%.     

Ferrimagnetic Behavior of meso-Tetrakis(2,3,5,6-tetrafluoro-4-methoxyphenyl)porphyrinatomanganese(iii) tetracyanoethenide, [MnTF4OMePP][tcne]⋅2 PhMe: Structural Evidence for a Second-Order Crystallographic Phase Transition

The quest to identify a new molecule-based magnet led to the discovery that the reduction of meso-tetrakis(pentafluorophenyl)porphyrinatomanganese(iii) chloride, Mn^IIITF₅PPCl, with sodium borohydride and its subsequent reaction with tetracyanoethylene (TCNE) forms the magnet [Mn^IIITF₄OMePP][tcne]. The structure undergoes a reversible phase transition (see picture) below −100 °C, which is not evident from either the magnetic or infrared data.     

Cutting-edge Results on Energies and Catalysts at SPring-8

What is an industrial researcher expecting from the use of synchrotron radiation at SPring-8? It seems that there are two answers. One expectation is that he is able to explain convincingly to his customers a distinctive advantage of the developed product in a visible manner, and the other is that he investigates essential quality of materials by returning to the starting point when he is at a loss what to do in the process of his R&D; thus he can gain the opportunity of making a technical breakthrough in his R&D. This is because SPring-8 provides the most powerful synchrotron radiation currently available. As a result, a researcher can understand the chemical-bonding states of the material structure at the atomic and electronic levels by utilizing new analytical tools such as XAFS (X-ray Absorption Fine Structure) and XRD (X-ray Diffraction), etc.     

Asymptotic expansions of the distributions of the latent roots and the latent vector of the Wishart and multivariate F matrices

Asymptotic expansions of the joint distributions of the latent roots of the Wishart matrix and multivariate F matrix are obtained for large degrees of freedom when the population latent roots have arbitrary multiplicity. Asymptotic expansions of the distributions of the latent vectors of the above matrices are also derived when the corresponding population root is simple. The effect of normalizations of the vector is examined.     

Selective imaging of positively charged polar and nonpolar lipids by optimizing matrix solution composition

Previous studies have shown that matrix‐assisted laser desorption/ionization–imaging mass spectrometry (MALDI‐IMS) is useful for studying the distribution of various small metabolites, particularly lipids. However, in this technique, selective ionization of the target molecules is imperative, particularly when analyzing small molecules. Since the sample clean‐up procedures available for the MALDI‐IMS of small metabolites are limited, the tissue sample will contain numerous molecular species other than the target molecules. These molecules will compete for ionization resulting in severe ion suppression. Hence, it is necessary to develop and optimize a sample preparation protocol for the target molecules. In this study, through model experiments using reference compounds, we optimized the composition of the matrix solution used for positively charged lipids in terms of the concentration of the organic solvent and presence/absence of alkali metal salts. We demonstrated that a high concentration of organic solvent in the matrix solution favors the preferential detection of lipids over peptides. The presence of alkali metal salts in the matrix solution was favorable for the detection of polar lipids, while a salt‐free matrix solution was suitable for the detection of nonpolar lipids. Furthermore, potassium salts added to the matrix solution caused merging of various lipid adducts (adducts with proton, sodium, and potassium) into one single potassiated species. Using the optimized protocols, we selectively analyzed phosphatidylcholine (PC) and triacylglycerol (TG) with different fatty acid compositions in a rat kidney section. Copyright © 2009 John Wiley & Sons, Ltd.