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111.
The synthesis of unsymmetric functionalized pentacenes from 1,4-anthraquinones and functionalized isobenzofurans, which were prepared by transformation via C-H bond activation, was successfully accomplished. Examples of the synthesis of pentacenes with functional groups at the 5-position are still rare. These obtained functionalized pentacenes are highly soluble in hexane, toluene, and THF. 相似文献
112.
Kuninobu Y Tokunaga Y Kawata A Takai K 《Journal of the American Chemical Society》2006,128(1):202-209
A rhenium complex, [ReBr(CO)(3)(thf)](2), catalyzes the reaction of an aromatic aldimine with an isocyanate and an acetylene to give a phthalimidine and an indene derivative in a quantitative yield, respectively. The reactions proceed via C-H bond activation, insertion of the isocyanate or the acetylene, intramolecular nucleophilic cyclization to the aldimine of the generated amido- or alkenyl-rhenium species, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are usually employed in this type of reaction, the rhenium catalyst promotes the insertion of a polar unsaturated molecule. This occurs more easily than the insertion of a nonpolar unsaturated molecule. 相似文献
113.
Kuninobu Y Nishina Y Nakagawa C Takai K 《Journal of the American Chemical Society》2006,128(38):12376-12377
A rhenium complex, [ReBr(CO)3(thf)]2, catalyzed reactions of aromatic ketimines with aldehydes to give isobenzofuran derivatives in good to excellent yields. In contrast to ruthenium and rhodium catalysts, aldehydes, which are polar unsaturated molecules, inserted into the C-H bond after activation by the rhenium complex. 相似文献
114.
Direct asymmetric hydroxyamination reaction catalyzed by an axially chiral secondary amine catalyst 总被引:1,自引:0,他引:1
A direct asymmetric hydroxyamination reaction of aldehydes with nitrosobenzene was found to be catalyzed by the novel axially chiral secondary amine catalyst (S)-1d. The resulting optically enriched hydroxyamination products were readily converted to beta-amino alcohols or 1,2-diamines in one pot. 相似文献
115.
[reaction: see text] A concise method for the preparation of isochromene carboxylates has been developed by the regioselective 1,6-addition of various nucleophiles such as Grignard reagents, alkoxide, and cyanide onto benzopyranylidenetungsten(0) complexes, followed by iodine oxidation of the addition intermediates. 相似文献
116.
In the current work we present our preliminary evaluation of a new protein labeling strategy, namely oxidation labeling. We found that a bis(2-picolyl) amine analogue coordinating Cu+ was able to oxidize histidine to oxo-histedine in a small peptide by generating reactive oxygen species upon exposure to hydrogen peroxide. The bis(2-picolyl) amine unit was then incorporated into the natural product tautomycin via an oxime linker. The compound, which showed good activity toward protein phosphatase 1γ (PP1γ), will be used in oxidation labeling studies with PP1γ. 相似文献
117.
118.
Mitsuo Takai J. Ross Colvin 《Journal of polymer science. Part A, Polymer chemistry》1978,16(6):1335-1342
It is suggested that the transformation from cellulose I to cellulose II during mercerization is the result of a progressive shift of the sheets of cellulose chains within the crystallites of a microfibril from the quarter-staggered relation in cellulose I to complete correspondence in cellulose II. Qualitatively, the results of such a shift would be consistent with the observed increases in lateral disorder, changes in cell dimensions, swelling, changes in infrared absorption, increases in reactivity of hydroxyl groups and especially with changes in the relative intensities of meridional, x-ray diffraction reflections of cellulose fibers. The consequences of such a shift also include variations of the dihedral angle at the glycosidic linkage to provide an opportunity for the conformational changes which have been deduced from Raman and infrared spectra. Such a shift may take place in the transformation of native celluloses with antiparallel structure as well as those with parallel polarity. It is consistent with and is able to explain examples of “memory” of previous treatment in cellulose samples. 相似文献
119.
Sawada M Takai Y Yamada H Yoshikawa M Arakawa R Tabuchi H Takada M Tanaka J Shizuma M Hirose K Fukuda K Tobe Y 《European journal of mass spectrometry (Chichester, England)》2004,10(1):27-37
Chiral recognition in the host-guest complexation systems of chiral crown ether hosts and amino ester guests was thoroughly examined using the electrospray ionization (ESI) mass spectrometry/enantiomer labeled (EL)-guest method. In this method, the mass spectra of a mixture of three components in a solution, a chiral host (H), an equal amount of an (S)-enantiomer guest labeled with deuterium atoms (G(S-dn)(+)) and an unlabeled (R)-enantiomer guest (G(R)+), were measured and the relative peak intensity value [I(H + G(R))(+) / I(H + G(S-dn))(+) = IRIS] of the host-guest complex ions, observed with an excess guest concentration, was taken to provide the chiral recognition ability of the host. In our earlier report (1996), we demonstrated that the apparent chiral recognition abilities using a mass spectrometer with a homemade ESI interface were depressed by about one tenth compared with the corresponding abilities obtained by fast-atom bombardment (FAB) MS. In the present study, the enantioselective complexation behaviors of various combinations of chiral crown hosts with chiral guests were further investigated in detail mainly using a modern commercial ESI/ion trap (IT) mass spectrometer. Consequently, it was found that the apparent IRIS values from the ESI-MS/EL-guest method changed significantly, depending upon the instrument used, and in particular, upon the ESI interfaces. Moreover, under the specific measuring conditions in ESI-IT-MS, the degrees of depression of the apparent chiral recognition abilities are roughly grouped into three classes, depending upon the number (or probably the type) of the hydrophobic substituents of the hosts. Representing the degrees by the slopes when plotting the apparent IRIS values in ESI-MS versus those in FAB-MS, the slopes for the three classes are (1) 1.0, (2) 0.7 and (3) 0.3; the higher the hydrophobicity of the hosts (and then, the host-guest complex ions), the lower the slope (the apparent enantioselectivity). Strengthening the degree of depression may be caused by an increase in the local concentration of the host close to the surface of the droplets produced during the electrospary ionization process. The chiral recognition ability (K(R )/ K(S)) in an equilibrated solution agrees quite well with the IRIS value in FAB-MS rather than that in ESI-MS. 相似文献
120.
Nobuharu Goto Kotaro T. Yamamoto Masakatsu Watanabe 《Photochemistry and photobiology》1993,57(5):867-871
Abstract— An analysis was made by action spectroscopy, using the Okazaki Large Spectrograph, of the inhibition of hypocotyl elongation of wild-type plants and the hy2 mutant of Arabidopsis thaliana. Two day old etiolated seedlings were irradiated for 8 h with monochromatic light and left in the dark for 16 h before measurement of hypocotyl length. Spectrophotometric measurement showed that levels of phytochrome in the etiolated tissue of the hy2 mutant were less than 9% of those in the wild type. The action spectra of the wild type looked like those of high irradiance response and showed peaks at 375, 450, 625 and 725 nm, whereas the action spectra of hy2 showed only the peaks at 375 and 450 nm. Monochromatic light of wavelengths longer than 500 nm had no significant inhibitory effects on hy2 plants. Blue and UV-A light were about five times more effective in the wild type than in hy2 plants. Severe inhibitory effects were observed with UV-B light. It is concluded that inhibition of the growth of the hypocotyl involves combined actions of phytochrome and a putative blue/UV-A photoreceptor(s). 相似文献