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1.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
2.
Takumi Watanabe Yuichiro Nishizawa Haruka Minato Dr. Chihong Song Prof. Dr. Kazuyoshi Murata Prof. Dr. Daisuke Suzuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):8934-8938
The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications. 相似文献
3.
A p68 reductase participating in the asymmetric reduction of the C–C double bond of 2-substituted 2-butenolides was isolated from Marchantia polymorpha. The enzyme reduced 2-substituted 2-butenolides to give (R)-butanolides, and the reduction of citraconic anhydride afforded (R)-methylsuccinic anhydride. 相似文献
4.
Masaharu Asano Jinhua Chen Yasunari Maekawa Takahiro Sakamura Hitoshi Kubota Masaru Yoshida 《Journal of polymer science. Part A, Polymer chemistry》2007,45(13):2624-2637
A novel process comprising the UV‐induced photografting of styrene into poly(tetrafluoroethylene) (PTFE) films and subsequent sulfonation has been developed for preparing proton‐conducting membranes. Although under UV irradiation the initial radicals were mainly generated on the surface of the PTFE films by the action of photosensitizers such as xanthone and benzoyl peroxide, the graft chains were readily propagated into the PTFE films. The sulfonation of the grafted films was performed in a chlorosulfonic acid solution. Fourier transform infrared and scanning electron microscopy were used to characterize the grafted and sulfonated membranes. With a view to use in fuel cells, the proton conductivity, water uptake, and mechanical properties of the prepared membranes were measured. Even through the degree of grafting was lower than 10%, the proton conductivity in the thickness direction of the newly prepared membranes could reach a value similar to that of a Nafion membrane. In comparison with γ‐ray radiation grafting, UV‐induced photografting is very simple and safe and is less damaging to the membranes because significant degradation of the PTFE main chains can be avoided. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2624–2637, 2007 相似文献
5.
Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described. 相似文献
6.
A new method for rotation and brightness invariant pattern recognition was proposed by applying multiple circular harmonic expansions to the joint transform correlator. The amplitudes of the multiple orders of circular harmonic expansions made from a detecting image were synthetically modified to respond to the same auto-correlation peaks. These modified circular harmonic expansions were arranged in the input plane as reference patterns together with an arbitrary target pattern, and the correlation signals between them were calculated in the subtracted joint transform correlator. The fraction of the correlation-peak intensities between the target and the references were extracted as a new discrimination parameter. This new parameter performs pattern recognition under rotation and brightness invariance with good discriminability. Its high discriminability has been proved in computer simulations using the face image patterns of many individuals. 相似文献
7.
Katsumi Kubota 《Tetrahedron》2006,62(49):11397-11401
The first highly enantioselective silicon Lewis acid catalyst for an asymmetric organic transformation has been developed. The catalyst derives its activity from the strain induced in the silicon center by virtue of being constrained in a five-membered ring. A simple tridentate ligand has been developed and the derived chlorosilane complex catalyzes the Diels-Alder cycloaddition of methacrolein and cyclopentadiene with 94% ee. 相似文献
8.
H. Kobayashi T. Sakurai Y. Yamashita T. Kubota O. Maida M. Takahashi 《Applied Surface Science》2006,252(21):7700-7712
X-ray photoelectron spectroscopy (XPS) measurements under bias can observe low density interface states for metal-oxide-semiconductor (MOS) diodes with low densities. This method can give energy distribution of interface states for ultrathin insulating layers for which electrical measurements cannot be performed due to a high density leakage current. During the XPS measurements, a bias voltage is applied to the rear semiconductor surface with respect to the ∼3 nm-thick front platinum layer connected to the ground, and the bias voltage changes the occupation of interface states. Charges accumulated in the interface states shift semiconductor core levels at the interface, and thus the analysis of the bias-induced shifts of the semiconductor core levels measured as a function of the bias voltage gives energy distribution of interface states. In the case of Si-based MOS diodes, the energy distribution and density of interface states strongly depend on the atomic density of silicon dioxide (SiO2) layers and the interfacial roughness, respectively. All the observed interface state spectra possess peaked-structures, indicating that they are due to defect states. An interface state peak near the Si midgap is attributable to isolated Si dangling bonds at the interface, while those above and below the midgap to Si dangling bonds interacting weakly with Si or oxygen atoms in the SiO2 layers. A method of the elimination of interface states and defect states in Si using cyanide solutions has been developed. The cyanide method simply involves the immersion of Si in KCN solutions. Due to the high Si-CN bond energy of ∼4.5 eV, the bonds are not ruptured at 800 °C and upon irradiation. The cyanide treatment results in the improvement of the electrical characteristics of MOS diodes and solar cells. 相似文献
9.
Bortoletto D Goldberg M Horwitz N Mestayer MD Moneti GC Sharma V Shipsey IP Skwarnicki T Csorna SE Letson T Brock IC Ferguson T Artuso M Bebek C Berkelman K Blucher E Byrd J Cassel DG Cheu E Coffman DM Crawford G DeSalvo R DeWire JW Drell PS Ehrlich R Galik RS Gittelman B Gray SW Halling AM Hartill DL Heltsley BK Kandaswamy J Kowalewski R Kreinick DL Kubota Y Lewis JD Mistry NB Mueller J Namjoshi R Nandi S Nordberg E O'Grady C Peterson D Pisharody M Riley D Sapper M Silverman A Stone S Worden H 《Physical review letters》1989,62(21):2436-2439
10.
Alam MS Katayama N Kim IJ Li WC Lou XC Sun CR Bortoletto D Goldberg M Horwitz N Mestayer MD Moneti GC Sharma V Shipsey IP Skwarnicki T Csorna SE Letson T Brock IC Ferguson T Artuso M Bebek C Berkelman K Blucher E Byrd J Cassel DG Cheu E Coffman DM Crawford G DeSalvo R DeWire JW Drell PS Ehrlich R Galik RS Gittelman B Gray SW Halling AM Hartill DL Heltsley BK Kandaswamy J Kowalewski R Kreinick DL Kubota Y Lewis JD Mistry NB Mueller J Namjoshi R Nandi S Nordberg E O'Grady C Peterson D Pisharody M 《Physical review D: Particles and fields》1989,40(11):3790