Novel Chiral Bisformamide-Promoted Asymmetric Allylation of Benzaldehyde with Allyltrichlorosilane

Novel chiral bisformamides have been prepared from (R,R)-1,2-cyclohexanediamine and utilized as Lewis bases in the asymmetric allylation of benzaldehyde with allyltrichlorosilane. The reaction in the presence of Lewis base 1i gave an 83:17 enantiomeric ratio (R/S) of the products in 90% isolated yield.      

Synthesis of nearly micron-sized particles by soap-free emulsion polymerization of methacrylic monomer using an oil-soluble initiator

Methacrylic monomer was used in soap-free emulsion polymerization in order to obtain a stable dispersion containing particles of the polymerized monomer. 2,2′-Azobis(2-methylpropionitrile) (AIBN) or 1,1′-azobis(1-acetoxy-1-phenylethane) (OT_AZO-15) were used as the radical initiator. Although particles with a size of about 1.0 μm were obtained when using methyl methacrylate as the monomer and AIBN as the initiator, the particles did not exhibit good dispersion stability. When OT_AZO-15, which has phenyl rings, was used as the initiator, the monomer phase solidified instead of forming particles in the aqueous phase. Benzyl methacrylate (BMA) monomer, which contains a phenyl ring, was polymerized using AIBN. Negatively charged particles with a size of 0.90 μm were formed. These particles exhibited good dispersion stability probably because of the pi electrons of the phenyl ring in the BMA monomer. The method in this study allows the synthesis of nearly micron-sized particles without surfactant, organic solvent, and electrolyte.     

Application of Novel Glycosides Prepared with Odorless Benzenethiols in Glycosylation Reaction

p‐Dodecylbenzenethiol (1) and p‐octyloxybenzenethiol (2) were synthesized as new odorless benzenethiols. Moreover, preparation of novel 1‐thioglycosides using 1 and 2 as well as their application for glycosylation reactions was performed. As a result, it was found that these 1‐thio‐glycosides were excellent glycosyl donors, and especially 2‐thio‐sialoside prepared from 1 and 2 afforded the best result to date in terms of α‐ and β‐selectivity in the sialylation where only the single C‐3 hydroxyl group of acceptor D‐galactopyranoside was free. All procedures from the preparation of thioglycosides to glycosylation reaction were attainable under completely odorless conditions.     

Adsorption and photochemical behaviors of the novel cationic xanthene derivative on the clay surface

Novel tetra-cationic xanthene derivative (Flu) was synthesized. Its adsorption and photochemical behaviors on the clay surface were investigated. Fluorescence quantum yield (?_f) and fluorescence lifetime were 0.50 and 2.9 ns for Flu/clay complex. ?_f of Flu was enough high (>0.1) even at high density conditions (0.080 molecules nm⁻²). It is supposed that the strong interaction between clay and Flu by the ‘Size-Matching Effect’ realizes the highly emissive clay complexes at high density adsorption condition by a suppression of a molecular aggregation, which tends to decrease the photochemical activity.     

Multiple Reaction Pathways Operating in the Mechanism of Vinylogous Mannich‐Type Reaction Activated by a Water Molecule

A systematic search for reaction pathways for the vinylogous Mannich‐type reaction was performed by the artificial force induced reaction method. This reaction affords δ‐amino‐γ‐butenolide in one pot by mixing 2‐trimethylsiloxyfuran, imine, and water under solvent‐free conditions. Surprisingly, the search identified as many as five working pathways. Among them, two concertedly produce anti and syn isomers of the product. Another two give an intermediate, which is a regioisomer of the main product. This intermediate can undergo a retro‐Mannich reaction to give a pair of intermediates: an imine and 2‐furanol. The remaining pathway directly generates this intermediate pair. The imine and 2‐furanol easily react with each other to afford the product. Thus, all of these stepwise pathways finally converge to give the main product. The rate‐determining step of all five (two concerted and three stepwise) pathways have a common mechanism: concerted Si? O bond formation through the nucleophilic attack of a water molecule on the silicon atom followed by proton transfer from the water molecule to the imine. Therefore, these five pathways have comparable barriers and compete with each other.     

Phase structure of a U(1) lattice gauge theory with dual gauge fields

We introduce a U(1) lattice gauge theory with dual gauge fields and study its phase structure. This system is partly motivated by unconventional superconductors like extended s-wave and d  -wave superconductors in the strongly-correlated electron systems and also studies of the t–J$t\text{–}J$ model in the slave-particle representation. In this theory, the “Cooper-pair” (or RVB spinon-pair) field is put on links of a cubic lattice due to strong on-site repulsion between original electrons in contrast to the ordinary s  -wave pair field on sites. This pair field behaves as a gauge field dual to the U(1) gauge field coupled with the hopping of electrons or quasi-particles of the t–J$t\text{–}J$ model, holons and spinons. By Monte Carlo simulations we study this lattice gauge model and find a first-order phase transition from the normal state to the Higgs (superconducting) phase. Each gauge field works as a Higgs field for the other gauge field. This mechanism requires no scalar fields in contrast to the ordinary Higgs mechanism. An explicit microscopic model is introduced, the low-energy effective theory of which is viewed as a special case of the present model.     

The Sixth Painlevé Equation as Similarity Reduction of $${\widehat{\mathfrak{gl}}_3}$$ Generalized Drinfel’d–Sokolov Hierarchy

Scaling symmetry of -type Drinfel’d–Sokolov hierarchy is investigated. Applying similarity reduction to the hierarchy, one can obtain the Schlesinger equation with (n + 1) regular singularities. Especially in the case of n = 3, the hierarchy contains the three-wave resonant system and the similarity reduction gives the generic case of the Painlevé VI equation. We also discuss Weyl group symmetry of the hierarchy.      

Geometric analysis of anharmonic downward distortion following paths

A mathematical aspect of the anharmonic downward distortion following (ADDF) path is discussed. The ADDF method is utilized as an automated reaction path search method, which can explore transition state geometries on a potential energy surface from a potential minimum. We show that the maximum number of the ADD stationary paths intersecting the potential minimum is 2^{f + 1} ? 2 , where f denotes the degree of freedom of the system. We also show that the bifurcation of the ADD stationary path is essential to detect all the transition states connected from a given minimum. The ADDF computation is demonstrated for a H₂O molecule in which pitchfork bifurcation is observed.     

2′,4′-BNA/LNA with 9-(2-Aminoethoxy)-1,3-diaza-2-oxophenoxazine Efficiently Forms Duplexes and Has Enhanced Enzymatic Resistance**

Artificial nucleic acids are widely used in various technologies, such as nucleic acid therapeutics and DNA nanotechnologies requiring excellent duplex-forming abilities and enhanced nuclease resistance. 2′-O,4′-C-Methylene-bridged nucleic acid/locked nucleic acid (2′,4′-BNA/LNA) with 1,3-diaza-2-oxophenoxazine (BNAP ( B^H )) was previously reported. Herein, a novel B^H analogue, 2′,4′-BNA/LNA with 9-(2-aminoethoxy)-1,3-diaza-2-oxophenoxazine (G-clamp), named BNAP-AEO ( B^AEO ), was designed. The B^AEO nucleoside was successfully synthesized and incorporated into oligodeoxynucleotides (ODNs). ODNs containing B^AEO possessed up to 10⁴-, 152-, and 11-fold higher binding affinities for complementary (c) RNA than those of ODNs containing 2′-deoxycytidine ( C ), 2′,4′-BNA/LNA with 5-methylcytosine ( L ), or 2′-deoxyribonucleoside with G-clamp ( P^AEO ), respectively. Moreover, duplexes formed by ODN bearing B^AEO with cDNA and cRNA were thermally stable, even under molecular crowding conditions induced by the addition of polyethylene glycol. Furthermore, ODN bearing B^AEO was more resistant to 3′-exonuclease than ODNs with phosphorothioate linkages.