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41.
Mamoru Tobisu Toshifumi Morioka Akimichi Ohtsuki Naoto Chatani 《Chemical science》2015,6(6):3410-3414
The reductive cleavage of the C–O bonds of aryl ethers has great potential in organic synthesis. Although several catalysts that can promote the reductive cleavage of aryl ethers have been reported, all such systems require the use of an external reductant, e.g., hydrosilane or hydrogen. Here, we report the development of a new nickel-based catalytic system that can cleave the C–O bonds of ethers in the absence of an external reductant. The hydrogen atom required in this new reductive cleavage reaction is provided by the alkoxy group of the substrate, which serves as an internal reductant. The absence of an external reductant enables the unique chemoselectivity, i.e., the selective reduction of an alkoxy group over alkenes and ketones. 相似文献
42.
Hitoshi MomochiTakafumi Noguchi Toshifumi MiyagawaNaoki Ogawa Makoto TadokoroTsuyoshi Satoh 《Tetrahedron letters》2011,52(23):3016-3019
The reaction of lithium α-sulfinyl carbanion of enantiopure dichloromethyl p-tolyl sulfoxide with α,β-unsaturated carbonyl compounds gave optically active 1-chlorocyclopropyl p-tolyl sulfoxides having a carbonyl group with high asymmetric induction from the sulfur chiral center. Reduction of the carbonyl group followed by treatment with Grignard reagent, the 1-chlorocyclopropyl p-tolyl sulfoxides resulted in the formation of enantiopure allenic alcohols via the Doering-LaFlamme-type rearrangement of enantiopure cyclopropylmagnesium carbenoid intermediates. This is the first example for the asymmetric synthesis of allenes by the Doering-LaFlamme allene synthesis. 相似文献
43.
Benzynes were generated from o-(trimethylsilyl)phenols using nonafluorobutanesulfonyl fluoride (NfF) by a domino process, i.e., the nonaflation of the phenolic hydroxyl group of o-(trimethylsilyl)phenols by NfF followed by the attack of the produced fluoride ion on the trimethylsilyl group. The generated benzyne immediately underwent various reactions to give polysubstituted benzenes. 相似文献
44.
Toshifumi Inouchi Dr. Takuya Nakashima Dr. Masaya Toba Prof. Tsuyoshi Kawai 《化学:亚洲杂志》2011,6(11):3020-3027
T‐shaped π‐conjugated molecules with an N‐methyl‐benzimidazole junction have been synthesized and their acid‐responsive photophysical properties owing to the change in the π‐conjugation system are discussed. T‐shaped π‐conjugated molecules consist of two orthogonal π‐conjugated systems including a phenyl thiophene extended from the 2‐position and alkyl phenylenes connected through various π‐spacers from the 4,7‐positions of the N‐methyl‐benzimidazole junction. The π‐spacers, such as thiophene, ethyne, and ethane, have an effect on the acid response of photophysical properties in terms of changes in conformation, excited‐state energy and charge‐transfer (CT) characteristics. In particular, the π‐conjugated molecule with ethynyl spacers exhibited a marked redshift in the fluorescence spectrum with a large Stokes shift upon the addition of acid, whereas the other molecules showed substantial quenching. The redshift in emission was studied in detail by temperature‐dependent fluorescence measurements, which indicated the transition to a CT state over the finite activation energy at the excited state. The change in the frontier molecular orbitals upon acid addition was further discussed by means of DFT calculations. 相似文献
45.
Issei Otsuka Ryosuke Sakai Toshifumi Satoh Ryohei Kakuchi Harumi Kaga Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2005,43(23):5855-5863
A poly(phenylacetylene) bearing a polycarbohydrate ionophore as a graft chain (copolymer 4 ) was synthesized by the copolymerization of end‐functionalized (1→6)‐2,5‐anhydro‐3,4‐di‐O‐ethyl‐D ‐glucitol with a 4‐ethynylbenzoyl group (macromonomer 2 ) with phenylacetylene. Copolymer 4 showed a split‐type circular dichroism (CD) in the long absorption region of the conjugated polymer backbone (280–500 nm), and the CD pattern varied in response to external stimuli, such as the solvents and temperature. This suggested that 4 had a predominantly one‐handed helical conformation in the polyacetylene backbone. The CD pattern of 4 was completely inverted by the formation of a complex between the macromolecular ionophore units and the selected metal cations, that is, Ba2+, Pb2+, Sr2+, Na+, and Li+. This suggested that copolymer 4 underwent a helix–helix transition through the host–guest complexation with achiral inorganic metal cations. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5855–5863, 2005 相似文献
46.
Masashi Nakagawa Tatsuo Iwasa Satoshi Kikkawa Toshifumi Takao Yasutsugu Shimonishi Motoyuki Tsuda 《Photochemistry and photobiology》1997,65(1):187-191
Abstract— We determined the structure and site of fatty acid incorporated in octopus rhodopsin using a combination of fluorescence label and enzymatic cleavage methods in conjunction with fast-atom bombardment (FAB) mass spectrometry. A single peptide containing two adjacent cysteines, Cys337 and Cys338, was successfully isolated using the fluorescence from a dye conjugated to Cys345. The FAB mass spectrometric analysis of the peptide (323phe-340 phe) revealed that two palmitoyl groups are linked to Cys337 and Cys338 via thioester bonds in octopus rhodopsin as in bovine rhodopsin. 相似文献
47.
Toshifumi Miyazawa Toshihiko Otomatsu Takashi Yamada Shigeru Kuwata 《Tetrahedron letters》1984,25(7):771-772
Copper(II) chloride was found to be an extremely efficient additive suppressing racemization in the carbodiimide mediated couplings. 相似文献
48.
Okimichi Yano Susumu Saito Yoshio Sato Toshifumi Takeda Atsushi Tanaka Yasaku Wada 《Journal of Polymer Science.Polymer Physics》1981,19(2):221-227
The dielectric loss of high-density polyethylene was measured from 1 kHz to 100 MHz with the improved calorimetric method at liquid-helium temperature for samples with different oxidation times t. Two loss peaks, centered at ca. 4 kHz and at 1 MHz, both increase in height with increasing t. On the bases of these results along with previously reported ones, the low-frequency and high-frequency losses are ascribed to the tunneling of protons of OH groups in crystalline and amorphous regions, respectively. 相似文献
49.
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