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11.
Annulation of Alkynyl Aryl Ethers with Allyl Pivalates To Give 2,3‐Bismethylenechromanes through Double C−H Bond Cleavage 下载免费PDF全文
Dr. Yasunori Minami Megumi Sakai Tomohiro Anami Prof. Dr. Tamejiro Hiyama 《Angewandte Chemie (International ed. in English)》2016,55(30):8701-8705
The treatment of silylethynyloxyarenes with allylic pivalates in the presence of a palladium catalyst led to efficient C?H bond cleavage in both substrates and a novel annulation reaction to give 2,3‐bismethylenechromanes. When ortho‐allylated silylethynyloxybenzenes were used as the substrates, the same products were obtained. This result shows that site‐selective intramolecular hydrovinylation is involved in the annulation reaction. The synthetic utility of the products was demonstrated by the construction of condensed polycycles. 相似文献
12.
Hongyuan Wang Toshinari Ugomori Yong Wang Kazuhiro Tanaka Hidetoshi Kita Ken‐Ichi Okamoto Yasunori Suma 《Journal of Polymer Science.Polymer Physics》2000,38(13):1800-1811
Poly(ethylene oxide imide) segmented copolymer (PEO‐PI) membranes were crosslinked by the chemical reaction between ethylene glycol diglycidyl ether and benzylalcohol groups of diamine moieties in polyimide segments at high temperatures. Sorption and diffusion of penetrants took place in poly(ethylene oxide) segment microdomains. Sorption and desorption behavior of pure vapors such as benzene (Bz), cyclohexane (Cx) and n‐hexane (Hx) was classified as the Fickian diffusion. Sorption isotherms of binary liquid mixtures could be represented by the Flory–Rehner model, but the model overpredicted the sorption amounts of Cx and Hx, leading to small predictions of sorption selectivity αS for Bz/Cx and Bz/Hx systems. UNIFAC‐FV model fairly well predicted the sorption amounts of aromatic hydrocarbons, but significantly overestimated those of nonaromatic ones, leading to too small predictions of αS. Pervaporation (PV) behavior of PEO‐PI membranes was governed by sorption behavior followed by membrane swelling. Diffusion coefficient weakly depended on the minimum cross section of a penetrant. The diffusivity selectivity αD hardly depended on the feed composition and was about 1.4 and 0.75 for Bz/Cx and Bz/Hx, respectively. PV selectivity αPV was larger for Bz/Hx than for Bz/Cx because of larger αS. PEO‐PI membranes displayed high specific permeation flux Ql and reasonably high αPV for aromatic/nonaromatic hydrocarbons; for example, Ql = 60 Kg μm/(m2 h) and αPV = 8 for a feed mixture containing Bz, Tol, Hx, n‐Ot and i‐Ot of 20 wt % at 353 K. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1800–1811, 2000 相似文献
13.
Nakayama T Kurosawa Y Furui S Kerman K Kobayashi M Rao SR Yonezawa Y Nakano K Hino A Yamamura S Takamura Y Tamiya E 《Analytical and bioanalytical chemistry》2006,386(5):1327-1333
Polymerase chain reaction (PCR) is an essential part of research based on genomics or cell analysis. The development of a
microfluidic device that would be suitable for high-temperature-based reactions therefore becomes an important contribution
towards the integration of micro-total analysis systems (μTAS). However, problems associated with the generation of air bubbles
in the microchannels before the introduction of the assay liquid, which we call the “initial start-up” in this study, made
the flow irregular and unstable. In this report, we have tried to address these problems by adapting a novel liquid-flow method
for high-temperature-based reactions. A PDMS-based microfluidic device was fabricated by soft-lithography techniques and placed
on a cartridge heater. The generation of the air bubbles was prevented by introducing the fluorinated oil, an inert and highly
viscous liquid, as the cap just before the introduction of the sample solutions into the microchannels. The technique was
applied for continuous-flow PCR, which could perform PCR on-chip in a microfluidic system. For the evaluation of practical
accuracy, plasmid DNA that serves as a reference molecule for the quantification of genetically modified (GM) maize was used
as the template DNA for continuous-flow PCR. After PCR, the products were collected in a vial and analyzed by gel electrophoresis
to confirm the accuracy of the results. Additionally, quantitative continuous-flow PCR was performed using TaqMan technology
on our PCR device. A laser detection system was also used for the quantitative PCR method. We observed a linear relationship
between the threshold cycle (Ct) and the initial DNA concentration. These results showed that it would be possible to quantify
the initial copies of the template DNA on our microfluidic device. Accurate quantitative DNA analysis in microfluidic systems
is required for the integration of PCR with μTAS, thus we anticipate that our device would have promising potential for applications
in a wide range of research. 相似文献
14.
[reaction: see text] Ethyl 1-thio-2,3,4,6-tetrakis-O-triisopropylsilyl-beta-d-glucopyranoside, ethyl 6-O-benzyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-d-glucopyranoside, and ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-d-glucopyranoside induced highly beta-selective O-glucosidations. Among them, the 6-O-pivaloylated substrate provided the best selectivity up to alpha/beta = 3:97 with cyclohexylmethanol, and the substrate was used for glucosidations with secondary and tertiary alcohols in a highly beta-selective manner. The selectivity would be caused by the twist-boat conformation of the pyranose; this is the first beta-selective O-glucosidation based on conformational control of the pyranose ring. 相似文献
15.
DESIGN AND PERFORMANCE OF THE OKAZAKI LARGE SPECTROGRAPH FOR PHOTOBIOLOGICAL RESEARCH 总被引:7,自引:1,他引:7
Masakatsu WatanabeMasaki Furuya†Yasuhiro Miyoshi†Yasunori Inoue†Isao Iwahashi‡Koichi Matsumoto‡ 《Photochemistry and photobiology》1982,36(4):491-498
A computer-operated spectrograph was recently built at Okazaki, Japan. Different specimens can be placed on a horseshoe-shaped focal curve (10 m long) covering a wavelength range of 250 to 1000 nm so they can be irradiated simultaneously. The linear dispersion is about 0.8 nm/cm. The photon fluence rate on the focal curve is 5 x 1015 . photons x cm-2 x s-1 at 300nm and 1 x 1016 photons x cm-2 x s-1 at 600 and at 900 nm. The spectral half width is 5.5 nm or less on the focal curve. The stray light content is about 10-5 of the main peak at the peak wavelength ± 100 nm. Specimens are set in microcomputer-controlled threshold boxes so that wavelengths, photon fluence rates, photon fluences and timing of irradiations are controlled automatically according to a pre-programmed schedule. An optical fiber system is also provided for remote irradiations. 相似文献
16.
Yasunori Inoue Hiro-o Hamaguchi Kotaro T. Yamamoto Mitsuo Tasumi Masaki Furuya 《Photochemistry and photobiology》1985,42(4):423-427
Abstract— Fluorescence spectra of native rye phytochrome were determined under different light conditions at liquid nitrogen temperature. Fluorescence spectrum of the red-light-absorbing form (Pr) had a major peak at about 685 nm (14 600 cm−1 ) and a broad sub-peak at about 515 nm (19 400 cm−1 ). The peak height at 685 nm was reduced by irradiation with monochromatic light of 640 nm, and a new peak became obvious at about 702 nm (14250 cm−1 ). This spectral change was almost completely reversed by subsequent irradiation with 700-nm light. Fluorescence spectrum of the photoequilibrium mixture of Pr and far-red-light absorbing form under continuous red light showed a sharp peak at about 685 nm having a peak height ca. 12% of Pr, and a broad sub-peak at about 508 nm (19 700 cm−1 ). Light of 730 nm did not reduce the peak height at about 685 nm but induced a new shoulder at about 699 nm (14300 cm−1 ). Monochromatic light of 640 and 700 nm given following the light of 730 nm could not reverse the spectral change at 699 nm induced by the irradiation with 730-nm light. Fluorescence spectrum of Pr in partially degraded phytochrome was similar to that in native phytochrome but the peak position in the red region was shifted by about 5 nm (100 cm−1 ) to the blue. 相似文献
17.
Yasunori Yamamoto Dr. Kazunori Kurihara Dr. Norio Miyaura Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(24):4414-4416
Ligand design by‐pam : A ruthenium‐catalyzed asymmetric arylation of aldehydes with arylboronic acids has been developed, giving chiral diarylmethanols in good yields. The use of a chiral bidentate phosphoramidite ligand ((R,R)‐Me‐bipam) led to excellent enantioselectivities.
18.
A robust, practical synthesis of (20S)‐10‐(3‐aminopropyloxy)‐7‐ethylcamptothecin (T‐2513, 5 ), which is a water‐soluble analogue of camptothecin, has been developed. The key step in this synthesis is a highly diastereoselective ethylation at the C20 position by using N‐arylsulfonyl‐(R)‐1,2,3,4‐tetrahydroisoquinoline‐3‐carboxylic acid ester as a chiral auxiliary, which affords the key intermediate ethyl‐(S)‐2‐acyloxy‐2‐(6‐cyano‐5‐oxo‐1,2,3,5‐tetrahydroindolizin‐7‐yl)butanoate ( 8 k ) in 93 % yield and 87 % de. Optically pure compound 8 k was obtained by a single recrystallization from acetone and its further elaboration through Friedlander condensation afforded compound 5 . This synthesis does not require any chromatographic purification steps and can provide compound 5 on a multi‐gram scale in 6.3 % overall yield (16 steps). 相似文献
19.
Hiroyoshi Nakajima Katsuhiro Yamada Yuki Iseki Satoru Hosoda Ayako Hanai Yasunori Oumi Toshiharu Teranishi Tsuneji Sano 《Journal of polymer science. Part A, Polymer chemistry》2003,41(24):3324-3332
Polypropylene (PP)/Ti-MCM-41 nanocomposites were prepared by isospecific propylene polymerization with Ti-MCM-41/Al(i-C4H9)3 catalyst. The cross polarization/magic angle spinning (CP/MAS) 13C NMR spectrum of the composite was similar to that of the conventional isotactic PP, and the decrease in the pore volume of Ti-MCM-41 in the nanocomposites, as measured by N2 adsorption, was consistent with the value calculated from the weight loss in the thermogravimetric analysis (TGA) curve; both these facts attest to propylene polymerization within the mesopores of Ti-MCM-41. Alkali treatment followed by extraction with o-dichlorobenzene allows us to extract the confined PP out of the Ti-MCM-41 mesopores. Although the PP/Ti-MCM-41 nanocomposites do not exhibit a crystalline melting point, the same PP when extracted from the mesopores showed a clear melting point at 154.7 °C; this indicates that the crystallization of PP confined in mesopores is strongly hindered. For the PP polymerized within the confinement, the molecular weight (Mw) and molecular weight distribution (Mw/Mn) were 84,000 and 4.3, respectively; these values were considerably smaller than those of the PP polymerized concurrently outside the Ti-MCM-41 mesopores (Mw = 200,000–450,000, Mw/Mn = 40–75). Therefore, the confinement also has a marked effect on the molecular weight of the PP. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3324–3332, 2003 相似文献
20.
Prof. Dr. Yasunori Yamamoto Masaaki Yohda Tomohiko Shirai Prof. Dr. Hajime Ito Prof. Dr. Norio Miyaura 《化学:亚洲杂志》2012,7(10):2446-2449
A chiral O‐linked C2‐symmetric bidentate phosphoramidite (Me‐BIPAM) was found to be efficient for the ruthenium‐catalyzed addition of arylboronic acids to isatins. Asymmetric synthesis of 3‐aryl‐3‐hydroxy‐2‐oxindoles by 1,2‐addition of arylboronic acids to isatins was carried out in the presence of [RuCl2(PPh3)3]/(R,R)‐Me‐BIPAM and KF, resulting in an enantioselectivity as high as 90 % ee. It was found that the reaction with N‐protected isatins proceeds with high yields and good enantioselectivities. The best protective groups on the nitrogen atom were different depending on the substituents on the aromatic ring. The use of a N‐benzyl group resulted in excellent enantioselectivities in many substrates compared with other groups. 相似文献