Asymmetric benzoin condensation catalyzed by chiral rotaxanes tethering a thiazolium salt moiety via the cooperation of the component: can rotaxane be an effective reaction field?

Although some reactions on rotaxanes have been reported, the characteristic features of the rotaxanes providing unique reaction fields have hardly been studied, especially as catalyst. In our continuous studies on interlocked molecules such as rotaxanes and catenanes, we have noticed the importance of such interlocked structures with high freedom in functionalized materials such as molecular catalyst. For catalytic asymmetric benzoin condensations, two optically active rotaxanes possessing thiazolium salt moieties were prepared using the binaphthyl group as the chiral auxiliary. The benzoin condensations of aromatic aldehydes catalyzed by the chiral rotaxanes as catalysts gave optically active benzoins with ca. 30% ee in moderate to high chemical yields depending upon the structure of rotaxane and the reaction conditions employed. From the results, two intrarotaxane chirality transfers are confirmed: (i) through-space chirality transfer from wheel to axle and (ii) through-bond chirality transfer controlled with an achiral wheel. Because these asymmetric reaction fields are specific to the rotaxane structure, the importance and possibility of the "rotaxane field" as a particular reaction field is demonstrated in this work.     

Polymer-supported bisBINOL ligands for the immobilization of multicomponent asymmetric catalysts

[reaction: see text] Polymer-supported bisBINOL ligands were successfully utilized for the immobilization of multicomponent asymmetric catalysts. The polymer-supported Al-Li-bis(binaphthoxide) (ALB) catalyst was more effective than the dendrimer-supported ALB in the Michael reaction of 2-cyclohexen-1-one with dibenzyl malonate affording the adduct in 91% yield with 96% ee. The polymer was also effective for the immobilization of a mu-oxodititanium complex that promoted carbonyl-ene reaction of ethyl glyoxalate with alpha-methyl styrene to provide the adduct with up to 98% ee.     

DFT Study of a 5‐endo‐trig‐Type Cyclization of 3‐Alkenoic Acids by Using Pd–Spiro‐bis(isoxazoline) as Catalyst: Importance of the Rigid Spiro Framework for Both Selectivity and Reactivity

The reaction pathway of an enantioselective 5‐endo‐trig‐type cyclization of 3‐alkenoic acids catalyzed by a chiral palladium–spiro‐bis(isoxazoline) complex, Pd–SPRIX, has been studied by density functional theory calculations. The most plausible pathway involves intramolecular nucleophilic attack of the carboxylate moiety on the C?C double bond activated by Pd–SPRIX and β‐H elimination from the resulting organopalladium intermediate. The enantioselectivity was determined in the cyclization step through the formation of a π‐olefin complex, in which one of the two enantiofaces of the olefin moiety was selected. The β‐H elimination occurs via a seven‐membered cyclic structure in which the acetate ligand plays a key role in lowering the activation barrier of the transition state. In the elimination step, the SPRIX ligand was found to behave as a monodentate ligand due to the hemilability of one of the isoxazoline units thereby facilitating the elimination. Natural population analysis of this pathway showed that the more weakly electron‐donating SPRIX ligand, compared with the bis(oxazoline) ligand, BOX, facilitated the formation of the π‐olefin complex intermediate, leading to a smaller overall activation energy and a higher reactivity of the Pd–SPRIX catalyst.     

High-Pressure Synthesis of Fully Occupied Tetragonal and Cubic Tungsten Bronze Oxides

A high-pressure reaction yielded the fully occupied tetragonal tungsten bronze K₃W₅O₁₅ (K_0.6WO₃). The terminal phase shows an unusual transport property featuring slightly negative temperature-dependence in resistivity (dρ/dT<0) and a large Wilson ratio of R_W=3.2. Such anomalous metallic behavior possibly arises from the low-dimensional electronic structure with a van Hove singularity at the Fermi level and/or from enhanced magnetic fluctuations by geometrical frustration of the tungsten sublattice. The asymmetric nature of the tetragonal tungsten bronze K_xWO₃-K_0.6−yBa_yWO₃ phase diagram implies that superconductivity for x≤0.45 originates from the lattice instability because of potassium deficiency. A cubic perovskite KWO₃ phase was also identified as a line phase—in marked contrast to Na_xWO₃ and Li_xWO₃ with varying quantities of x (<1). This study presents a versatile method by which the solubility limit of tungsten bronze oxides can be extended.     

Biobased myo-inositol as nucleator and stabilizer for poly(lactic acid)

myo-Inositol made from a biomass feedstock was used as an additive for poly (l-lactic acid) (PLLA) which was also made from biomass feedstock. The crystallization and stabilization of PLLA by the addition of myo-inositol were evaluated by the melt injection molding process. While the isothermal crystallization of PLLA at 100 °C had finished over 14 min after melting, that of PLLA with 5 wt% myo-inositol finished within 2 min. The crystal growth of PLLA started when the myo-Inositol crystal was added, and the crystallization was promoted. Furthermore, the molecular weight of PLLA with myo-inositol did not decrease during the melt-mixed at 200 °C, different from that of PLLA without the myo-inositol. myo-Inositol prevented the degradation of PLLA during the thermal melting process. The biomass carbon ratio measured by the accelerator mass spectroscopy method showed that the PLLA with 5 wt% myo-inositol was a fully biobased material. It was demonstrated that myo-inositol was a multi-functional biobased additive for the modification of PLLA without decreasing its mechanical properties.     

Large-scale forcing with less communication in finite-difference simulations of stationary isotropic turbulence

This study proposes a new forcing scheme suitable for massively-parallel finite-difference simulations of stationary isotropic turbulence. The proposed forcing scheme, named reduced-communication forcing (RCF), is based on the same idea as the conventional large-scale forcing scheme, but requires much less data communication, leading to a high parallel efficiency. It has been confirmed that the RCF scheme works intrinsically in the same manner as the conventional large-scale forcing scheme. Comparisons have revealed that a fourth-order finite-difference model run in combination with the RCF scheme (FDM-RCF) is as good as a spectral model, while requiring less computational costs. For the range 80 < Re_λ < 540, where Re_λ is the Taylor microscale-based Reynolds number, large computations using the FDM-RCF scheme show that the Reynolds dependences of skewness and flatness factors have similar power-laws as found in previous studies.     

Synthesis and healing properties of poly(arylether sulfone)–poly(alkylthioether) multiblock copolymers containing disulfide bonds

Thermoplastic elastomers composed of soft and hard segments are important elastic and processable synthetic polymers. The microphase‐separated soft domains show low glass transition temperature and possess sufficient chain mobility at room temperature. In this study, we report the synthesis and healing properties of multiblock copolymers containing disulfide bonds as dynamic covalent bonds. The multiblock copolymers composed of poly(arylether sulfone) and poly(alkylthioether) segments were synthesized by oxidative coupling polymerization of the corresponding thiol‐terminated oligomers. Atomic force microscopy phase images, differential scanning calorimetry, and dynamic mechanical analysis curves indicated the microphase‐separated morphology of the multiblock copolymer. Self‐healing properties of the polymer were evaluated by changes in the elongation at break of the cut/adhered samples. The elongation recovery increased with UV irradiation time, and the multiblock copolymer showed a 93% recovery after UV irradiation for 5 h. The healing efficiency induced by UV irradiation, determined by subtracting the recovery without UV irradiation, was calculated to be 51%. According to the UV spectra and solubility changes after UV irradiation, the main healing factor in this study was the crosslinking reactions caused by thiyl radicals generated from UV irradiation instead of disulfide exchange reactions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3545–3553