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Haruka Takeuchi Prof. Dr. Shinsuke Inuki Kohei Nakagawa Takaaki Kawabe Dr. Atsuhiko Ichimura Prof. Dr. Shinya Oishi Prof. Dr. Hiroaki Ohno 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21396-21401
We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radical ipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses. 相似文献
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Dr. Yasuyuki Yamada Hayato Iida Shinya Shibano Dr. Nozomi Mihara Prof. Tatsuhisa Kato Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(37):e202200819
Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linkage. We found that closely stacking two π systems requires bridging alkyl chains above a certain length, and the shorter bridges hinder stacking because of their lower flexibility. The stacking distance between porphyrin and phthalocyanine in the conjugate with decyl (C10) chains was estimated to be 4.03 Å and showed a unique physical character arising from short-distance interactions. The longer alkyl chains minimized steric restriction inside the fourfold rotaxane and allowed efficient communication between the porphyrin and phthalocyanine units. This is due to the flexibility of the side chains. 相似文献
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Dr. Hua Zhang Prof. Dr. Shinya Hagihara Prof. Dr. Kenichiro Itami 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(47):16796-16800
The dimethylamino (Me2N) group is arguably the most versatile functional group capable of highly efficient and site‐selective directed aromatic functionalizations at the ortho‐, meta‐, and para‐positions depending on reaction conditions. While the repertoire of Me2N‐directed reactions is growing at a rapid pace, the lack of a general method to transform this group to other functionalities hampers its wider application in organic synthesis. Here we report nickel‐catalyzed C?N borylations of aryl‐ and benzyl‐dimethylamines that permit the conversion of a huge library of largely underutilized Me2N‐containing organic molecules into various functional molecules by taking advantage of the wealth of existing C?B functionalization methods. 相似文献
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Ryohei Yoshisaki Dr. Shinya Kimura Dr. Masashi Yokoya Prof. Dr. Masamichi Yamanaka 《化学:亚洲杂志》2021,16(14):1937-1941
Maltose is a ubiquitous disaccharide produced by the hydrolysis of starch. Amphiphilic ureas bearing hydrophilic maltose moiety were synthesized via the following three steps: I) construction of urea derivatives by the condensation of 4-nitrophenyl isocyanate and alkylamines, II) reduction of the nitro group by hydrogenation, and III) an aminoglycosylation reaction of the amino group and the unprotected maltose. These amphiphilic ureas functioned as low molecular weight hydrogelators, and the mixtures of the amphipathic ureas and water formed supramolecular hydrogels. The gelation ability largely depended on the chain length of the alkyl group of the amphiphilic urea; amphipathic urea having a decyl group had the highest gelation ability (minimum gelation concentration=0.4 mM). The physical properties of the supramolecular hydrogels were evaluated by measuring their thermal stability and dynamic viscoelasticity. These supramolecular hydrogels underwent gel-to-sol phase transition upon the addition of α-glucosidase as a result of the α-glucosidase-catalyzed hydrolysis of the maltose moiety of the amphipathic urea. 相似文献
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Makoto Shimizu Takato Kawamura Shinya Fukumoto Isao Mizota Yusong Zhu 《Journal of heterocyclic chemistry》2021,58(3):751-756
The ketene silyl acetal derived from ethyl 2-benzyltetrahydroisoquinoline-1-carboxylate undergoes a rapid oxidation reaction with N-bromosuccinimide to form 3,4-dihydroisoquinolinium ion, which reacts with Grignard reagents to give 1,1-disubstituted tetrahydroisoquinolines in good yields. 相似文献
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Yokokita Takuya Yano Shinya Komori Yukiko Haba Hiromitsu 《Journal of Radioanalytical and Nuclear Chemistry》2022,331(2):1127-1134
Journal of Radioanalytical and Nuclear Chemistry - To investigate sulfate complex formation of Rf, we performed batch-wise ion-exchange experiments of its homologues Zr and Hf and its pseudo... 相似文献
9.
The walk of animals is achieved by the interaction between the dynamics of their mechanical system and the central pattern generator (CPG). In this paper, we analyze dynamic properties of a simple walking model of a biped robot driven by a rhythmic signal from an oscillator. In particular, we examine the long-term global behavior and the bifurcation of the motion that leads to chaotic motion, depending on the model parameter values. The simple model consists of a hip and two legs connected at the hip through a rotational joint. The joint is driven by a rhythmic signal from an oscillator, which is an open loop. In order to analyze the bifurcation, we first obtained approximate solutions of the walking motion and then constructed discrete dynamics using the Poincaré map. As a result, we found that consecutive period-doubling bifurcations occur as the model parameter values change, and that the walking motion leads to chaotic motion over the critical value of the model parameters. Moreover, we approximately obtained the period-doubling solutions and the critical value by employing a Newton-Raphson method. Our analytical results were verified by the numerical simulations. 相似文献
10.
Visible light‐mediated radical alkenylation of benzylsulfonium salts was achieved by means of fac‐Ir(ppy)3 as a photocatalyst, giving allylbenzenes as products. A variety of functional groups, such as halogen, ester, and cyano, were well tolerated in this transformation. Starting benzylsulfonium salts could be readily prepared from benzyl alcohols by an acid‐mediated substitution, increasing the synthetic utility of this transformation. 相似文献