Enantioselective addition of terminal alkynes to aldehydes catalyzed by a Cu(I)-TRAP complex

The addition of terminal alkynes to aromatic aldehydes was carried out under mild conditions in the presence of a Cu-phosphine complex, which was prepared in situ from Cu(O-t-Bu) and TRAP chiral bisphosphine, to yield enantiomerically enriched propargyl alcohols with moderate enantioselectivities. Furthermore, according to stoichiometric reactions, the reaction presumably involves the addition of a TRAP-coordinated Cu(I) acetylide to an aldehyde.     

Internal delivery of soft chlorine and bromine atoms: stereoselective synthesis of (E)-beta-halogenovinyl(aryl)-lambda3-iodanes through domino lambda3-iodanation-1,4-halogen shift-fluorination of alkynes

4-(Difluoroiodo)toluene-induced domino lambda(3)-iodanation-1,4-halogen shift-ring enlargement-fluorination reaction of 5-halopentynes with a four-, five-, or six-membered carbocycle afforded the ring-expanded (E)-delta-fluoro-beta-halovinyl-lambda3-iodanes stereoselectively in high yields, probably via the intermediacy of five-membered halonium ions. Use of internal alkynes makes it possible to synthesize tetrasubstituted beta-halovinyl-lambda(3)-iodanes with defined stereochemistry.     

Mass transfer of weak acid in nanometer-sized pores of octadecylsilyl-silica gel

The sorption of bromophenol blue or anthracene-9-carboxylic acid as a weak acid into single octadecylsilyl (ODS)-silica gel microparticles in a solution was analyzed by microcapillary injection-manipulation and absorption microspectroscopy. The distribution ratio and the sorption rate were highly dependent on the pH of the solution. These results are discussed in terms of the acid dissociation/association, distribution between the ODS and solution phases, and intraparticle diffusion of the weak acid in the nanometer-sized pores of the ODS-silica gel.     

Concise total synthesis of (-)-spongotine A

The first asymmetric total synthesis of spongotine A is described. The oxidative synthesis of the imidazoline/ketone unit from keto aldehyde and diamine is a key step in this synthesis. The absolute stereochemistry of the asymmetric center of natural spongotine A is revealed as the (S)-configuration.     

Heterodyne Interferometers Using Orthogonally Polarized and Two-Frequency Shifted Light Sources with Super-high Extinction Ratio

This paper describes heterodyne interferometers using orthogonally polarized and two-frequency shifted light sources of two types with super-high extinction ratio to reduce non-linearity of the interferometer due to polarization cross-talk. The acousto-optic modulators are used to shift light frequency. In the first interferometer the light source with Glan-Thomson prisms of very high extinction ratio (50 dB) is used to make the polarization cross-talk very small. In the second interferometer the light source of two-frequency shifted beams with small crossing angle (2.5 rnrad-10 mrad) is used to completely exclude non-linearity of the interferometer due to polarization cross-talk. By measuring the thickness of vacuum evaporation film, it was demonstrated that the interferometers are useful to measure thickness of a thin film in nanometer order.     

Preferential orientation of crystallites spatially confined in lamellar microdomains of polyethylene‐block‐[atactic poly(propylene)]

Synchrotron small angle X‐ray scattering (SAXS), wide angle X‐ray scattering (WAXS), and transmission electron microscopy were carried out for an oriented polyethylene‐block‐[atactic poly(propylene)] with a molecular weight of 1.13×10⁵ and a volume fraction of polyethylene of 0.5. Isothermal crystallization at 93°C did not destroy the pre‐formed microdomain, however, with a higher crystallization temperature, the microdomain was more heavily deformed and more crystalline lamella grew. In WAXS profiles, preferential orientation of (020) reflection peak was observed, indicating that the crystalline lamella grew in parallel with the micro domain interface.     

Efficient Method for the Elongation of the N‐Acetylglucosamine Unit by Combined Use of Chitinase and β‐Galactosidase

A novel strategy for the regio‐ and stereoselective synthesis by two enzymatic steps of oligosaccharides having an N‐acetylglucosamine unit at the nonreducing end was developed. The first step involves a chitinase‐catalyzed highly selective β‐N‐acetyllactosamination of an oligosaccharide acceptor with a 4,5‐dihydrooxazole derivative of N‐acetyllactosamine as the glycosyl donor. The usage of a transition‐state‐analogue substrate for the chitinase under basic conditions allows the reaction to proceed only in the synthetic direction while suppressing hydrolysis of the product in aqueous media. Several chitinase mutants also catalyzed the glycosylation efficiently under neutral conditions. The second step is a regioselective cleavage of the glycosidic bond between the terminal galactose unit and the adjacent N‐acetylglucosamine unit by the action of a β‐galactosidase. This constitutes a very useful method to add an N‐acetylglucosamine unit to the nonreducing end of chito‐ and cello‐oligosaccharide derivatives in a regio‐ and stereoselective manner.