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131.
Reductive Cross‐Coupling of Conjugated Arylalkenes and Aryl Bromides with Hydrosilanes by Cooperative Palladium/Copper Catalysis
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Dr. Kazuhiko Semba Kenta Ariyama Dr. Hong Zheng Ryohei Kameyama Prof. Dr. Shigeyoshi Sakaki Prof. Dr. Yoshiaki Nakao 《Angewandte Chemie (International ed. in English)》2016,55(21):6275-6279
A method for the reductive cross‐coupling of conjugated arylalkenes and aryl bromides with hydrosilanes by cooperative palladium/copper catalysis was developed, thus resulting in the highly regioselective formation of various 1,1‐diarylalkanes, including a biologically active molecule. Under the applied reaction conditions, high levels of functional‐group tolerance were observed, and the reductive cross‐coupling of internal alkynes with aryl bromides afforded trisubstituted alkenes. 相似文献
132.
Dr. Haiwang Lai Changming Jin Dr. Junsu Park Dr. Ryohei Ikura Prof. Yoshinori Takashima Prof. Makoto Ouchi 《Angewandte Chemie (International ed. in English)》2023,62(14):e202218597
In this study, we designed a methacrylate molecule with an alkyl-substituted trichloro salicylic acid pendant as a transformable bulky monomer to enable the synthesis of an alternating copolymer of methyl methacrylate (MMA) and n-butyl acrylate (nBA). The adamantyl-substituted methacrylate monomer ( 1-Ad ) showed very low homopolymerization propensity in radical polymerizations, but afforded the alternating copolymer with nBA via copolymerization. The 1-Ad units in the resultant copolymer were quantitatively and selectively transformed into MMA via transesterification with methanol to yield the alternating copolymer of MMA and nBA. Its alternating sequence was clearly demonstrated by a structural analysis via 13C NMR spectroscopy as well as the low reactivity ratios for the 1-Ad and nBA pair. Finally, we verified the superior self-healing ability of the alternating copolymer compared to that of the corresponding 1 : 1 statistical copolymer. 相似文献
133.
The efficient selective synthesis of secondary and tertiary amines has been achieved by means of Cp*Ir-catalyzed multialkylation of ammonium salts with alcohols without solvent: the reactions of ammonium acetate with alcohols gave tertiary amines exclusively, while those of ammonium tetrafluoroborate afforded secondary amines selectively. Using this method, secondary 5- and 6-membered cyclic amines were synthesized from ammonium tetrafluoroborate and diols in one pot. 相似文献
134.
Benzonorcorrole NiII Complexes: Enhancement of Paratropic Ring Current and Singlet Diradical Character by Benzo‐Fusion
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Takuya Yoshida Kohtaro Takahashi Yuki Ide Dr. Ryohei Kishi Jun‐ya Fujiyoshi Sangsu Lee Yuya Hiraoka Prof. Dr. Dongho Kim Prof. Dr. Masayoshi Nakano Prof. Dr. Takahisa Ikeue Prof. Dr. Hiroko Yamada Prof. Dr. Hiroshi Shinokubo 《Angewandte Chemie (International ed. in English)》2018,57(8):2209-2213
Fused benzene rings to antiaromatic compounds generally improve their stability but attenuate their antiaromaticity. The opposite case is now reported. NiII benzonorcorroles were synthesized and the effect of benzo‐fusion on the antiaromaticity was elucidated. The benzo‐fusion resulted in significant decrease of the HOMO–LUMO gaps and enhancement of the paratropic ring current effect. Furthermore, the introduction of the benzo groups induced singlet diradical character in the antiaromatic porphyrinoid. 相似文献
135.
Microalgae were screened from seawater for greenhouse gas CO2 fixation and d-lactic acid production by self-fermentation and tested for their growth rate, starch content, and conversion rate from starch
into d-lactic acid. More than 300 strains were isolated, and some of them were found to have suitable properties for this purpose.
One of the best strains, Nannochlorum, sp. 26A4, which was isolated from Sakito Island, had a starch content of 40% (dry weight), and a conversion rate from consumed
starch into d-lactic acid of 70% in the dark under anaerobic conditions. The produced d-lactic acid showed a high optical purity compared with the conventional one. The proposed new d-lactic acid production system using Nannochlorum sp. 26A4 should also be an effective technology for greenhouse gas CO2 fixation and/or conversion into industrial raw materials. 相似文献
136.
137.
Toshifumi Satoh Masaki Tamaki Tsukasa Taguchi Hideki Misaka Nguyen To Hoai Ryosuke Sakai Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2011,49(11):2353-2365
The cationic ring‐opening multibranching polymerization of 2‐hydroxymethyloxetane ( 1 ) as a novel latent AB2‐type monomer was carried out using trifluoromethane sulfonic acid or trifluoroboron diethyl etherate by a slow‐monomer‐addition (SMA) method. The polymer yield of poly‐1 ranged from ca. 58–88%, which increase with the increasing monomer addition time on the SMA method. The absolute molecular weights (Mw,MALLS) and the polydispersities of poly‐1 were in the range of 8,000–43,500 and 1.45–4.53, respectively, which also increased with the increasing monomer addition time. The Mark‐Houwink‐Sakurada exponents α in 0.2 M NaNO3 aq. were determined to be 0.02–0.25 for poly‐1 , indicating that poly‐1 has compact forms in the solution because of the highly branched structure. The degree of the branching value of poly‐1 , which was calculated by Frey's equation, ranged from ca. 0.50 to 0.58, which increased with the increasing monomer addition time. The steady shear flow of poly‐1 in aqueous solution exhibited a Newtonian behavior with steady shear viscosities independent of the shear rate. The results of the MALLS, NMR, and viscosity measurements indicated that poly‐1 is composed of a highly branched structure, i.e., the hyperbranched poly (2‐hydroxymethyloxetane). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
138.
Atsushi Narumi Harumi Kaga Kosei Kawasaki Yasuo Taniguchi Toshifumi Satoh Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2001,39(23):4061-4067
Glucosyl styrene ( 1a ), maltosyl styrene ( 1b ), and maltohexaosyl styrene ( 1c ) were prepared by the glycosylation of 4‐vinylbenzyl alcohol with the corresponding glycosyl trichloroacetimidates with boron trifluoride diethyl ether complex. The copolymerizations of 1a – 1c with styrene were carried out with 2,2′‐azobis(2‐methylpropionitrile) as an initiator in dry N,N‐dimethylformamide at 60 °C, and this was followed by deacetylation to produce amphiphilic polystyrenes with glucose ( 3a ), maltose ( 3b ), and maltohexaose ( 3c ) as hydrophilic segments. 3 showed various solubility characteristics that were dependent on the content of glucose residues, especially within a range of 20–50 wt %. The solubility characteristics of 3 , related to the copolymer composition, indicated that the hydrophilic property was remarkably improved with an increased number of glucose units, that is, in the order 3a < 3b ? 3c . The results described in this article provide useful information for the design of glycoconjugated architectures with desired amphiphilic properties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4061–4067, 2001 相似文献
139.
Dr. Akihito Konishi Koki Horii Haruna Iwasa Yui Okada Dr. Ryohei Kishi Prof. Dr. Masayoshi Nakano Prof. Dr. Makoto Yasuda 《化学:亚洲杂志》2021,16(12):1553-1561
The singlet open-shell character and antiaromaticity are intriguing features in π-conjugated carbocycles. These two exhibit similar chemical and physical properties. However, they rarely coexist in the same molecule. Understanding the interrelation between the open-shell and antiaromatic characteristics in the same molecule is crucial to control the electronic properties. Herein we describe the synthesis and characterization of a new member of diareno[a,f]pentalene, benzo[a]naphtho[2,3-f]pentalene 6 . Unlike its isomer 5 with a closed-shell ground state, 6 exhibits an appreciable open-shell character and a moderate antiaromatic feature. The behaviors of the open-shell index (y0) against the difference of the proton chemical signal (Δδ(H1)) between pentalenide dianions/neutral pentalenes for our reported pentalenes 1 , 4 , 5 , and 6 give a thought-provoking conclusion about the interrelation between open-shell and antiaromatic characteristics in this series. The mode of the incorporated quinoidal moiety and the formal molecular symmetry are critical to balance these two characteristics. 相似文献
140.
Artificial odorant sensors generally perform poorer than olfactory systems in living organisms. The excellent performances of living odorant systems are achieved by the molecular recognition abilities of odorant receptors and the neuronal information processing that follows. To take advantages of this, here we propose a novel hybrid odorant biosensor by means of expressing ionotropic odorant receptors of insects into dissociated neuronal cultures of rodents. This combination of materials brings significant advantages such as easy functional expression, prolonged lifetime, and an ability to amplify the weak ionic currents of odorant receptors. In the present work, pheromone receptors and co-receptors of silkmoth, i.e., BmOR1 and BmorOrco, were expressed in neuronal cultures via liposome transfection. Consequently, BmOR1 and BmorOrco were co-expressed in 8% of neuronal cells, and both receptors were co-localized on a cell membrane. In Ca++ imaging experiments, synchronous increase of calcium signals at the presentation of BOL was found in both transfected cells and non-transfected cells in a dose-dependent manner. These results provide the proof-of-concept of the proposed hybrid odorant biosensor. 相似文献