Highly enantioselective synthesis of atropisomeric anilide derivatives through catalytic asymmetric N-arylation: conformational analysis and application to asymmetric enolate chemistry

In the presence of (R)-DTBM-SEGPHOS-Pd(OAc)(2) catalyst, N-arylation (aromatic amination) of various o-tert-butylanilides with p-iodonitrobenzene proceeds with high enantioselectivity (88-96% ee) to give atropisomeric N-(p-nitrophenyl)anilides having an N-C chiral axis in good yields. Atropisomeric anilide products highly prefer to exist as the E-rotamer which has trans-disposed o-tert-butylphenyl group and carbonyl oxygen. The application of the present catalytic enantioselective N-arylation to an intramolecular version gives atropisomeric lactam derivatives with high optical purity (92-98% ee). The reaction of the lithium enolate prepared from the atropisomeric anilide and lactam products with various alkyl halides gives alpha-alkylated products with high diastereoselectivity (diastereomer ratio = 13:1 to 46:1).     

The burning rate’s effect on the flame length of weak fire whirls

This paper discusses why the visibly-determined flame length of a weak fire whirl increases as compared with the corresponding pool fire without spin. Here, a fire whirl is called weak when the pure aerodynamic effect of flow circulation has a negligible influence on the flame length. Split cylinders were used to apply a flow circulation to a 3-cm-diameter methane burner flame and a 3-cm-diameter ethanol pool fire. After applying the flow circulation, the flame length of the ethanol pool fire increased about three times, while little change was observed in the flame length of the methane burner flame. The difference is explained by the fact that the burning rate of the methane burner flame was fixed constant, whereas that of the ethanol pool fire increased due to the increased heat input to the fuel surface caused by a change in flame shape pushed toward the fuel surface. The experimental observations thus demonstrate that the burning-rate effect can significantly increase the flame length even under a weak circulation condition. Computational fluid dynamics (CFD) simulations were conducted to understand the detailed flow structure of a fire whirl. An analytical model was then developed based on the experimental observations and CFD calculations; the predicted relationship between the flame height and the burning rate agreed with experimental data.     

Polarimetry of short-pulse gamma rays produced through inverse Compton scattering of circularly polarized laser beams

We have developed a polarimetry of ultrashort pulse gamma rays based on the fact that gamma rays penetrating in the forward direction through a magnetized iron carry information on the helicity of the original gamma rays. Polarized, short-pulse gamma rays of (1.1+/-0.2)x10(6)/bunch with a time duration of 31 ps and a maximum energy of 55.9 MeV were produced via Compton scattering of a circularly polarized laser beam of 532 nm off an electron beam of 1.28 GeV. The first demonstration of asymmetry measurements of short-pulse gamma rays was conducted using longitudinally magnetized iron of 15 cm length. It is found that the gamma-ray intensity is in good agreement with the simulated value of 1.0x10(6). Varying the degree of laser polarization, the asymmetry for 100% laser polarization was derived to be (1.29+/-0.12)%, which is also consistent with the expected value of 1.3%.     

Conceptual defects of modern stereochemistry. Comprehensive remedy by stereoisograms based on RS-stereoisomerism for mediating between enantiomerism and stereoisomerism

The recognition of chirality as a single kind of handedness is a conceptual defect of modern stereochemistry, which has caused serious confusion in its theoretical foundations and stereochemical nomenclature. To remedy this defect, RS-stereogenicity is developed as another kind of handedness. These two kinds of handedness are integrated to give RS-stereoisomerism, which is formulated diagrammatically by stereoisograms. During the process of the remedy, the lack of the concept of ligand reflections has been revealed as another conceptual defect. The lack of the concept of orbits (equivalence classes) has been found to be one more defect, which has caused a misleading classification of isomers. By adopting the concept of orbits, the revised hierarchy of isomerism is developed, i.e., isomers $?$ isoskeletomers $?$ stereoisomers $?$ RS-stereoisomers $?$ enantiomers $?$ 3D-structures. Thereby, the theoretical foundations of modern stereochemistry are restructured rationally.     

Self-assembling process of zirconium oxide suspension induced by vaporization of volatile solvents

We investigated the self-assembling processes of solutions of poly(vinyl methyl ether) in mixed solvents of 2-butanone and water with and without zirconium oxide (ZrO₂) particles with average size of 75 nm during vaporization of the solvents by means of optical microscopy. The self-assembling processes can be classified into three regimes: (1) early stage (nucleation and growth regime), (2) intermediate stage (regularly arranged regime), and (3) late stage (aggregation and coalescence regime). In the intermediate stage, the water droplets, including the ZrO₂ particles, were regularly arranged with an almost constant spacing. The mechanism of the self-assembling processes is discussed on the basis of experimental results.

Meta-Tree Random Forest: Probabilistic Data-Generative Model and Bayes Optimal Prediction

This paper deals with a prediction problem of a new targeting variable corresponding to a new explanatory variable given a training dataset. To predict the targeting variable, we consider a model tree, which is used to represent a conditional probabilistic structure of a targeting variable given an explanatory variable, and discuss statistical optimality for prediction based on the Bayes decision theory. The optimal prediction based on the Bayes decision theory is given by weighting all the model trees in the model tree candidate set, where the model tree candidate set is a set of model trees in which the true model tree is assumed to be included. Because the number of all the model trees in the model tree candidate set increases exponentially according to the maximum depth of model trees, the computational complexity of weighting them increases exponentially according to the maximum depth of model trees. To solve this issue, we introduce a notion of meta-tree and propose an algorithm called MTRF (Meta-Tree Random Forest) by using multiple meta-trees. Theoretical and experimental analyses of the MTRF show the superiority of the MTRF to previous decision tree-based algorithms.     

Symmetry-itemized enumeration of quadruplets of RS-stereoisomers. II. The partial-cycle-index method of the USCI approach combined with the stereoisogram approach

The symmetry-itemized enumeration of quadruplets of stereoisograms is discussed by starting from a tetrahedral skeleton, where the partial-cycle-index (PCI) method of the unit-subduced-cycle-index approach (Fujita in Symmetry and combinatorial enumeration of chemistry. Springer, Berlin, 1991) is combined with the stereoisogram approach (Fujita in J Org Chem 69:3158–3165, 2004, Tetrahedron 60:11629–11638, 2004). Such a tetrahedral skeleton as contained in the quadruplet of a stereoisogram belongs to an RS-stereoisomeric group denoted by $\mathbf{T}_{d\widetilde{\sigma }\widehat{I}}$ , where the four positions of the tetrahedral skeleton accommodate achiral and chiral proligands to give quadruplets belonging to subgroups of $\mathbf{T}_{d\widetilde{\sigma }\widehat{I}}$ according to the stereoisogram approach. The numbers of quadruplets are calculated as generating functions by applying the PCI method. They are itemized in terms of subgroups of $\mathbf{T}_{d\widetilde{\sigma }\widehat{I}}$ , which are further categorized into five types. Quadruples for stereoisograms of types I–V are ascribed to subgroups of $\mathbf{T}_{d\widetilde{\sigma }\widehat{I}}$ , where their features are discussed in comparison between RS-stereoisomeric groups and point groups.