Asymmetric organocatalytic oxy-Michael addition of alcohols to α,β-unsaturated aldehydes

A 1,4-addition of alcohols to α,β-unsaturated aldehydes was found to be efficiently promoted by biphenyldiamine-based catalyst 3 without formation of the acetals. An asymmetric variant of this reaction has also been performed by designing a novel axially chiral organocatalyst (R)-10c.     

Cyclotron resonance and mass enhancement by electron correlation in KFe2As2

Cyclotron resonance (CR) measurements for the Fe-based superconductor KFe(2)As(2) are performed. One signal for CR is observed, and is attributed to the two-dimensional α Fermi surface at the Γ point. We found a large discrepancy in the effective masses of CR [(3.4±0.05)m(e) (m(e) is the free-electron mass)] and de Haas-van Alphen results, a direct evidence of mass enhancement due to electronic correlation. A comparison of the CR and de Haas-van Alphen results shows that both intra- and interband electronic correlations contribute to the mass enhancement in KFe(2)As(2).     

Catalytic asymmetric syntheses of isoxazoline-N-oxides under phase-transfer conditions

Catalytic asymmetric syntheses of various isoxazoline-N-oxides have been accomplished by asymmetric phase-transfer conjugate addition of bromomalonate to nitroolefins and subsequent ring-closing O-alkylation.     

Enzymatic Syntheses of N-Acetyllactosamine and N-Acetylallolactosamine by the Use of β-D-Galactosidases

Abstract

A β-D-galactosidase from Bacillus circulans induced β-D-galactopyranosyl transfer from lactose predominantly to a secondary (OH-4) rather than the primary hydroxyl group (OH-6) of 2-acetamido-2-deoxy-D-glucopyranose. 4-O-β-D-Galacto-pyranosyl-2-acetamido-2-deoxy-D-glucopyranose (N-acetyl-lactosamine) was thus readily synthesized on a gram scale and conveniently isolated by chromatography on a column of charcoal-Celite. On the other hand, the glycosyl transfer to the 6-position predominantly was efficiently induced to give 6-O-β-D-galactopyranosyl-2-acetamido-2-deoxy-D-glucopyranose (N-acetyl-allolactosamine) by consecutive use of β-D-galactosidases from Kluyveromyces lactis and B. circulans. These enzyme reactions were efficient enough to allow the one-pot preparation of the desired disaccharides.     

Synthesis of Aromatic Polythioethers Containing 1,3,5-Triazine Ring by Aromatic Nucleophilic Substitution Polymerization

Abstract

Reaction of 2,4-dichloro-6-phenyl-1,3,5-triazines with bis(4-mercaptophenyl) sulfide in the presence of a base in THF afforded the corresponding condensation polymer as a whole aromatic polythioether in moderate yield. The polymerization of several 2,4-dichloro-1,3,5-triazine derivatives with this dithiols also proceeded in the o-dichlorobenzene-water two-phase system by using phase transfer catalysts. The resulting polymers consisted of THF-soluble and -insoluble fractions. The x-ray diffraction pattern indicated that these THF-insoluble polymers have a highly crystalline nature. Further, the polymers obtained here showed high thermal stability.     

Gold and platinum catalyzed cascade reaction of propargyl acetates bearing terminal alkynes or methyl ketones

A gold (III)-catalyzed cascade reaction of propargyl acetates bearing an extra terminal alkyne (1) afforded γ-keto esters 3 and lactones 4. These products should be generated through allenyl ketone intermediate B via a 1,2-acyloxy cyclization/fragmentation/cycloisomerization/hydrolysis sequence. On the other hand, the cascade reaction of α-acetoxy ketones bearing terminal alkynes 5 afforded lactone 6 via allenyl ketone intermediate A. This reaction involves a [3,3]-sigmatropic acyloxy rearrangement/cycloisomerization/hydrolysis sequence.     

Supramolecular network formation through inclusion complexation of an α‐cyclodextrin‐based molecular tube

The supramolecular network formation through inclusion complexation between α‐cyclodextrin‐based molecular tube (MT) and poly(ethylene oxide) monocetylether‐graft‐dextran (5C₁₆PEO‐g‐Dex40) was demonstrated. From isothermal titration calorimetric (ITC) measurement, it was confirmed that MT formed an inclusion complex with two C₁₆PEO side chains in 5C₁₆PEO‐g‐Dex40. From viscosity measurements, the specific viscosity of the solution containing MT and 5C₁₆PEO‐g‐Dex40 was much larger than that containing 5C₁₆PEO‐g‐Dex40. It is considered that MT participates in the supramolecular network formation of 5C₁₆PEO‐g‐Dex40 through inclusion complexation with two C₁₆PEOs grafted to independent Dex40s.     

Synthesis and surface characterization of novel perfluorooctyl-functionalized polymers with well-defined architectures

We have successfully synthesized two kinds of novel well-defined chain-end-functionalized polystyrenes with one, two, three, and four perfluorooctyl (C₈F₁₇) groups and structurally analogous block copolymers, poly[styrene-b-4-(3-perfluoroocyl)propoxystyrene], by means of living anionic polymerization, followed by the Williamson reaction with C₈F₁₇(CH₂)₃Br. The surface properties and compositions of the films prepared from both C₈F₁₇-functionalized polymers have been characterized by contact angles using water and dodecane droplets and angle-dependent XPS measurement. It was observed that C₈F₁₇ groups were segregated and preferentially enriched at their topmost surfaces and the extent of the enrichment increased with the number of C₈F₁₇ group. The dependence of extent of C₈F₁₇ group enrichment on fluorine content however appears to be different between chain-end-functionalized polymer and block copolymer.