Researcher Database
Last Updated :2024/11/20
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Degree
Profile and Settings
Name (Japanese)
AshikariName (Kana)
YosukeName
X-3660-2019, 201901011021209047
Alternate Names
Achievement
Awards
- 2020/11 有機合成化学協会 関東化学 研究企画賞
バイメタリックアレーン類のフローマイクロ合成と金属選択的カップリング反応への展開受賞者: 芦刈洋祐 - 2013/04 日本化学会 第93春季年会学生講演賞
- 2008/06 第32回有機電子移動化学討論会 優秀ポスター賞
Published Papers
- Kazuhiro Okamoto, Dong‐eun Yoo, Rikako Yoshioka, Ryohei Nakasato, Yosuke Ashikari, Kenji Kitayama, Aiichiro NagakiAngewandte Chemie International Edition 2024/11/16
- Kazuhiro Okamoto, Dong‐eun Yoo, Rikako Yoshioka, Ryohei Nakasato, Yosuke Ashikari, Kenji Kitayama, Aiichiro NagakiAngewandte Chemie 2024/11/16
- Hiromichi V. Miyagishi, Yusuke Kimuro, Yosuke Ashikari, Aiichiro NagakiOrganic Letters 2024/06/14
- Hiroki Soutome, Hiroki Yamashita, Yutaka Shimizu, Masahiro Takumi, Yosuke Ashikari, Aiichiro NagakiNature Communications 15 (1) 2024/06/13Abstract In biosynthesis multiple kinds of reactive intermediates are generated, transported, and reacted across different parts of organisms, enabling highly sophisticated synthetic reactions. Herein we report a convergent synthetic approach, which utilizes dual intermediates of cationic and carbanionic species in a single step, hinted at by the ideal reaction conditions. By reactions of unsaturated precursors, such as enamines, with a superacid in a flow microreactor, cationic species, such as iminium ions, are generated rapidly and irreversibly, and before decomposition, they are transported to react with rapidly and independently generated carbanions, enabling direct C-C bond formation. Taking advantage of the reactivity of these double reactive intermediates, the reaction take place within a few seconds, enabling synthetic reactions which are not applicable in conventional reactions.
- Yosuke Ashikari, Takashi Tamaki, Kyosuke Tomite, Yuya Yonekura, aiichiro nagaki2024/05/17To accelerate advancements in organic chemistry research and development, we propose a fully automated system based on real-time inline analysis performed by Fourier-transform infrared spectroscopy and assisted by a neural network model. To rapidly collect data, a linear combination of spectral intensities was used as training data for a yield prediction model. Using this model, we demonstrated real-time yield prediction of Suzuki-Miyaura cross-coupling with remarkable accuracy. By combining this yield prediction model with real-time inline analysis and a flow chemistry setup, we have developed a fully automated system for the rapid and efficient optimization of reaction conditions and process analysis.
- Hiroki Soutome, Kei Maekawa, Yosuke Ashikari, Aiichiro NagakiOrganic Process Research & Development 2024/05/17
- Kazuhiro Okamoto, Dong-eun Yoo, Rikako Yoshioka, Ryohei Nakasato, Yosuke Ashikari, Kenji Kitayama, aiichiro nagaki2024/04/15
- Yosuke Ashikari, Rikako Yoshioka, Yuya Yonekura, Dong‐eun Yoo, Kazuhiro Okamoto, Aiichiro NagakiChemistry – A European Journal 2024/03/25
- Kazuhiro Okamoto, Kensuke Muta, Hidetaka Yamada, Ryosuke Higuma, Yosuke Ashikari, Aiichiro NagakiReaction Chemistry & Engineering 2024
- 機械学習を活用したフローリアクター合成のプロセス最適化、自動化芦刈洋祐, 永木愛一郎MATERIAL STAGE 23 (9) 41 - 45 2023/12 [Refereed][Invited]
- Hiroki Soutome, Yusuke Kimuro, Tomoko Kawaguchi, Dong-eun Yoo, Yiyue Yao, Shuto Oshida, Hiroki Nakayama, Masatomo Iwata, Ruka Ebisawa, Ryuhei Kikuchi, Kyosuke Tomite, Shuto Wada, Yosuke Ashikari, Aiichiro NagakiSynthesis 0039-7881 2023/11/28 [Refereed]
Abstract 4-Bromopyridine is a building block that can be converted into valuable compounds, but due to its low stability, it is commercially available in the form of hydrochloride salt. Therefore, the hydrochloride salt is usually desalted with a basic aqueous solution and dried before organic reaction. In this study, to simplify the preparation and reaction procedure of 4-bromopyridine, multiple operations, desalting with a base, separation of the aqueous layer, and subsequent halogen–lithium exchange reaction were integrated into a single flow reaction. The reaction sequence was completed within 20 seconds and the yields were higher than the conventional methods. This is because the subsequent reaction can be performed immediately after the generation of 4-bromopyridine, which is unstable under ambient conditions. - Yosuke Ashikari, Kyoko Mandai, Yiyue Yao, Yuta Tsuchihashi, Aiichiro NagakiChemElectroChem 10 (23) 2196-0216 2023/09/12 [Refereed]
Abstract We developed an electrocatalytic reduction of (hetero)aryl halides under mild conditions using a proton exchange membrane (PEM) reactor. This approach allows substituting the halogeno groups on the aryl rings to protons by water and electron. Taking advantage of this transformation, deuterodehalogenation of (hetero)aryl halides, which forms mono‐deuterated (hetero)aryls, was demonstrated using heavy water as a deuterium source. The current efficiency and deuterium ratio could be increased by the conditions optimized by machine‐learning method, Bayesian optimization. - Yosuke Muranaka, Taisuke Maki, Daiki Nakayoshi, Shusaku Asano, Katsuya Ikebata, Aiichiro Nagaki, Yosuke Ashikari, Kyoko Mandai, Kazuhiro MaeChemical Engineering Journal 469 143891 - 143891 1385-8947 2023/08 [Refereed][Not invited]
- Kazuhiro Okamoto, Ryosuke Higuma, Kensuke Muta, Keita Fukumoto, Yuta Tsuchihashi, Yosuke Ashikari, Aiichiro NagakiChemistry – A European Journal 29 (47) 0947-6539 2023/07/18 [Refereed][Not invited]
Abstract In this study, incorporation of one deuterium atom was achieved by H−D exchange of one of the two identical methylene protons in various dihalomethanes (halogen=Cl, Br, and I) through a rapid‐mixing microflow reaction of lithium diisopropylamide as a strong base and deuterated methanol as a deuteration reagent. Generation of highly unstable carbenoid intermediate and suppression of its decomposition were successfully controlled under high flow‐rate conditions. Monofunctionalization of diiodomethane afforded various building blocks composed of boryl, stannyl, and silyl groups. The monodeuterated diiodomethane, which served as a deuterated C1 source, was subsequently subjected to diverted functionalization methods to afford various products including biologically important molecules bearing isotope labelling at specific positions and homologation products with monodeuteration. - Yosuke Ashikari, Kaiteng Guan, Aiichiro NagakiFrontiers in Chemical Engineering 4 2022/07/22 [Refereed]
We achieved an integration of a lithiation of aryl bromides, a zincation of thus-generated aryllithiums, and a Negishi coupling of the arylzinc with an aryl halide in one flow. Taking advantages of flow microreactors, biaryls bearing a wide range of functional groups, especially biaryls bearing multiple electrophilic-functionalities were synthesized. - Yosuke Ashikari, Kei Maekawa, Masahiro Takumi, Noriyuki Tomiyasu, Chiemi Fujita, Kiyoshi Matsuyama, Riichi Miyamoto, Hongzhi Bai, Aiichiro NagakiCatalysis Today 388-389 231 - 236 0920-5861 2022/04 [Refereed][Invited]
- Yosuke Ashikari, Takashi Tamaki, Yusuke Takahashi, Yiyue Yao, Mahito Atobe, Aiichiro NagakiFrontiers in Chemical Engineering 3 819752 2022/01 [Refereed][Invited]
Owing to its applicability in sustainable engineering, flow electrochemical synthesis in a proton-exchange membrane (PEM) reactor has attracted considerable attention. Because the reactions in PEM reactors are performed under electro-organic and flow-synthetic conditions, a higher number of reaction parameters exist compared to ordinary reactions. Thus, the optimization of such reactions requires significant amounts of energy, time, chemical and human resources. Herein, we show that the optimization of alkyne semihydrogenation in PEM reactors can be facilitated by means of Bayesian optimization, an applied mathematics strategy. Applying the optimized conditions, we also demonstrate the generation of a deuterated Z-alkene. - フローマイクロケミストリーに基づく反応集積化永木愛一郎, 芦刈洋祐ケミカルタイムス 2022/01 [Refereed][Invited]
- Yosuke Ashikari, Kei Maekawa, Mai Ishibashi, Chiemi Fujita, Kiyonari Shiosaki, Hongzhi Bai, Kiyoshi Matsuyama, Aiichiro NagakiGreen Processing and Synthesis 10 (1) 722 - 728 2191-9542 2021/11/18 [Refereed]
Abstract Owing to their recyclability, heterogeneous transition metal catalysts represent a means of conserving depletable resources for the synthesis of pharmaceutical, agricultural, and functional chemicals. We recently developed a novel heterogeneous palladium catalyst and demonstrated its synthetic availability for Suzuki–Miyaura cross-coupling. Herein, we report the further application of the present catalyst to cross-coupling reactions in batch and flow, as well as a hydrogenative reduction reaction in flow. We demonstrate the flow synthesis for useful material, a liquid crystal, and a 1 h sequential operation of the coupling reaction and hydrogenation reaction. - フロー高速合成とAI活用の将来展望について永木愛一郎, 芦刈洋祐, 宅見正浩化学工学 85 (11) 611 - 614 2021/10 [Refereed][Invited]
- Yosuke Ashikari, Takashi Tamaki, Tomoko Kawaguchi, Mai Furusawa, Yuya Yonekura, Susumu Ishikawa, Yusuke Takahashi, Yoko Aizawa, Aiichiro NagakiChemistry – A European Journal 27 (65) 16107 - 16111 0947-6539 2021/09/22 [Refereed][Not invited]
- Mutsuo Nuriya, Yosuke Ashikari, Takanori Iino, Takuya Asai, Jingwen Shou, Keiko Karasawa, Kaho Nakamura, Yasuyuki Ozeki, Yukari Fujimoto, Masato YasuiAnalytical Chemistry 93 (27) 9345 - 9355 2021/07/01 [Refereed][Not invited]
The dopaminergic system is essential for the function of the brain in health and disease. Therefore, detailed studies focused on unraveling the mechanisms involved in dopaminergic signaling are required. However, the lack of probes that mimic dopamine in living tissues, owing to the neurotransmitter's small size, has hampered analysis of the dopaminergic system. The current study aimed to overcome this limitation by developing alkyne-tagged dopamine compounds (ATDAs) that have a minimally invasive and uniquely identifiable alkyne group as a tag. ATDAs were established as chemically and functionally similar to dopamine and readily detectable by methods such as specific click chemistry and Raman scattering. The ATDAs developed here were verified as analogue probes that mimic dopamine in neurons and brain tissues, allowing the detailed characterization of dopamine dynamics. Therefore, ATDAs can act as safe and versatile tools with wide applicability in detailed studies of the dopaminergic system. Furthermore, our results suggest that the alkyne-tagging approach can also be applied to other small-sized neurotransmitters to facilitate characterization of their dynamics in the brain. - Yosuke Ashikari, Aiichiro NagakiSynthesis 53 (11) 1879 - 1888 0039-7881 2021/01/18 [Refereed][Invited]
Aryl–aryl cross-coupling reactions are important reactions for the production of various biaryl compounds. This short review covers the various aryl–aryl cross-coupling reactions carried out in flow, focusing on the metal species of the aryl nucleophiles used in the cross-coupling reactions. - Yosuke Ashikari, Takashi Tamaki, Masahiro Takumi, Aiichiro NagakiTopics in Medicinal Chemistry 1862-2461 2021 [Refereed][Invited]
- Aiichiro Nagaki, Yosuke Ashikari, Masahiro Takumi, Takashi TamakiChemistry Letters 50 (3) 485 - 492 0366-7022 2020/12/17 [Refereed][Invited]
Organolithium reagents are often too unstable to use due to being highly reactive. This limits their application in organic synthesis. This review highlights our approach to various synthetic reactions mediated by organolithium reagents based on flash chemistry conducted in flow reactors, especially utilizing space-integration of the flow reactions. - Yiyuan Jiang, Yosuke Ashikari, Kaiteng Guan, Aiichiro NagakiSYNLETT 31 (19) 1937 - 1941 0936-5214 2020/10 [Refereed]
We herein report that flow microreactors can promote an efficiency of radical chain reactions. The chain reactions with a fast propagation step can be accelerated by virtue of an efficient heat-transfer character of the microreactors, whereas the yield of those reactions with a slow propagation step was increased by flow microreactors. Moreover, the yield was further increased by a sequential addition of the initiators, which was allowed by a flow-sequential-addition system. - Yosuke Ashikari, Tomoko Kawaguchi, Kyoko Mandai, Yoko Aizawa, Aiichiro NagakiJournal of the American Chemical Society 142 (40) 17039 - 17047 0002-7863 2020/08/28 [Refereed][Not invited]
- Yusuke Takahashi, Yosuke Ashikari, Masahiro Takumi, Yutaka Shimizu, Yiyuan Jiang, Ryosuke Higuma, Susumu Ishikawa, Hodaka Sakaue, Ibuki Shite, Kei Maekawa, Yoko Aizawa, Hiroki Yamashita, Yuya Yonekura, Marco Colella, Renzo Luisi, Toshihiro Takegawa, Chiemi Fujita, Aiichiro NagakiEUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2020 (5) 618 - 622 1434-193X 2020/02 [Refereed][Not invited]
In a flow microreactor, aryllithiums bearing a piperidylmethyl group were generated using nBuLi by precise residence time control and effective temperature control, and then selectively borylated with boronic esters such as 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (BpinOiPr) and trimethyl borate B(OMe)(3) by fast mixing. Moreover, the direct integration with Suzuki-Miyaura cross coupling were successfully achieved to obtain nitrogen-containing biaryl compounds. The present method could be applied for the straightforward synthesis of the key intermediate of a bioactive component bearing a piperidylmethyl-biphenyl framework. - Daisuke Ichinari, Yosuke Ashikari, Kyoko Mandai, Yoko Aizawa, Jun-ichi Yoshida, Aiichiro NagakiANGEWANDTE CHEMIE-INTERNATIONAL EDITION 59 (4) 1567 - 1571 1433-7851 2020/01 [Refereed][Not invited]
A novel straightforward method for aryl azides having functional groups based on generation and reactions of aryllithiums bearing a triazene group from polybromoarenes using flow microreactor systems was achieved. The present approach will serve as a powerful method in organolithium chemistry and open a new possibility in the synthesis of polyfunctional organic azides. - Kyoko Mandai, Yuta Tsuchihashi, Yousuke Ashikari, Jun-ichi Yoshida, Aiichiro NagakiTETRAHEDRON LETTERS 61 (2) 0040-4039 2020/01 [Refereed][Not invited]
The synthesis of O-18-labeled enantioenriched compounds and their facile evaluation system to determine enantiomeric excess (ee) using mass spectroscopy was described. Equimolar mixture of O-18-labeled and non-labeled pseudo-enantiomers were used as a substrate for enzyme-catalyzed kinetic resolution. Ees determined by mass spectroscopy showed good agreement with those by HPLC. Our method would be a promising tool for fast evaluation of ee and contribute to development of enantioselective transformations. (C) 2019 Published by Elsevier Ltd. - Tsuyoshi Yamada, Aya Ogawa, Hayato Masuda, Wataru Teranishi, Akiko Fujii, Kwihwan Park, Yosuke Ashikari, Noriyuki Tomiyasu, Tomohiro Ichikawa, Riichi Miyamoto, Hongzhi Bai, Kiyoshi Matsuyama, Aiichiro Nagaki, Hironao SajikiCatalysis Science & Technology 10 (18) 6359 - 6367 2044-4753 2020 [Refereed][Not invited]
Two different types of palladium catalysts supported on dual-pore monolithic silica beads [5% Pd/SM and 0.25% Pd/SM(sc)] for chemoselective hydrogenation were developed.
- Yosuke Ashikari, Kodai Saito, Toshiki Nokami, Jun-ichi Yoshida, Aiichiro NagakiCHEMISTRY-A EUROPEAN JOURNAL 25 (67) 15239 - 15243 0947-6539 2019/12 [Refereed][Not invited]
The present study describes the cationic oxo-thiolation of polymerizable alkenes by using highly reactive cationic species generated by anodic oxidation. These highly reactive cations were able to activate alkenes before their polymerization. Fast mixing in flow microreactors effectively controlled chemoselectivity, enabling higher reaction temperatures. - Yosuke Ashikari, Yukari Fujimoto, Masato Yasui, Mutsuo NuriyaProceedings for Annual Meeting of The Japanese Pharmacological Society 92 (0) 3 - O 2019 [Refereed][Not invited]
- Ryutaro Hayashi, Akihiro Shimizu, Yetao Song, Yosuke Ashikari, Toshiki Nokami, Jun-ichi YoshidaCHEMISTRY-A EUROPEAN JOURNAL 23 (1) 61 - 64 0947-6539 2017/01 [Refereed][Not invited]
Electrochemical oxidation of toluene derivatives in the presence of N-tosyldiphenylsulfilimine gave the corresponding benzylaminosulfonium ions, which were treated with tetrabutylammonium iodide under non-electrolytic conditions to give N-tosylbenzylamines. The transformation serves as a metal-and chemical-oxidant-free method for benzylic C-H amination. Because of high oxidation potential of N-tosyldiphenylsulfilimine the present method can be applied to synthesis of various benzylamines from functionalized toluene derivatives. - Laura Murphy, Damian Dunford, Adam Goetz, Kelli Ogawa, Yosuke Ashikari, Andrew BoydstonABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 252 0065-7727 2016/08 [Refereed][Not invited]
- Jun-ichi Yoshida, Akihiro Shimizu, Yosuke Ashikari, Tatsuya Morofuji, Ryutaro Hayashi, Toshiki Nokami, Aiichiro NagakiBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 88 (6) 763 - 775 0009-2673 2015/06 [Refereed][Not invited]
Reaction integration which combines multiple reactions in a single operation in one pot or in a flow system without isolating intermediates enhances the power and speed of organic synthesis to meet future demands for synthesis of various organic molecules. This article provides a brief outline of a new field of organic synthesis based on time integration and space integration of reactions using unstable reactive cationic intermediates generated by electrochemical oxidation. - Akihiro Shimizu, Ryutaro Hayashi, Yosuke Ashikari, Toshiki Nokami, Jun-ichi YoshidaBEILSTEIN JOURNAL OF ORGANIC CHEMISTRY 11 1860-5397 2015/02 [Refereed][Not invited]
beta-Haloalkoxysulfonium ions generated by the reaction of electrogenerated Br+ and I+ ions stabilized by dimethyl sulfoxide (DMSO) reacted with sodium hydroxide and sodium methoxide to give the corresponding halohydrins and epoxides, respectively, whereas the treatment with triethylamine gave alpha-halocarbonyl compounds. - Yosuke Ashikari, Yohei Kiuchi, Tomoya Takeuchi, Koji Ueoka, Seiji Suga, Jun-ichi YoshidaCHEMISTRY LETTERS 43 (2) 210 - 212 0366-7022 2014/02 [Refereed][Not invited]
The reaction of electrochemically generated N-acyliminium ion pools with alkenes bearing a heteroatom nucleophilic functionality such as a hydroxy group, a carboxy group, and an oxime moiety led to intermolecular carbon carbon bond formation followed by intramolecular carbon heteroatom bond formation to give the corresponding heterocyclic compounds such as cyclic ethers, lactones, and 2-isoxazolines, respectively. - Jun-ichi Yoshida, Yosuke Ashikari, Kouichi Matsumoto, Toshiki NokamiJOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN 71 (11) 1136 - 1144 0037-9980 2013/11 [Refereed][Not invited]
The "cation pool" method involves the generation and accumulation of highly reactive organic cations in solution. These can serve as powerful carbon and heteroatom electrophiles in organic synthesis. Recent developments in the cation pool method including the indirect cation pool method, cation chain reactions, and integrated electrochemical-chemical reactions are described. - Yosuke Ashikari, Akihiro Shimizu, Toshiki Nokami, Jun-ichi YoshidaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 135 (43) 16070 - 16073 0002-7863 2013/10 [Refereed][Not invited]
Halogen and chalcogen cations (X+ = Br+, I+, ArS+, and ArSe+) were generated by low-temperature electrochemical oxidation in the presence of dimethyl sulfoxide (DMSO) and were accumulated in the solution. DFT calculations indicated that DMSO stabilizes these cations by coordination. The complexes of I+ with one and two DMSO molecules were observed by cold-spray-ionization MS analyses. The stability of the resulting cation pools of X+ increased in the order of Br+ < I+ < ArS+ < ArSe+, which could be explained in terms of the electronegativity of X. The cation pools served as versatile reagents for organic synthesis; the reactions with alkenes gave beta-X-substituted alkoxysulfonium ions, which were converted to the corresponding carbonyl compounds by the treatment with triethylamine, whereas the treatment with methanol gave the corresponding alcohols. The reactions with aminoalkenes and 1,6-dienes gave the cyclized products. - Kouichi Matsumoto, Tomonari Sanada, Hayato Shimazaki, Kazuaki Shimada, Shino Hagiwara, Shunsuke Fujie, Yosuke Ashikari, Seiji Suga, Shigenori Kashimura, Jun-ichi YoshidaASIAN JOURNAL OF ORGANIC CHEMISTRY 2 (4) 325 - 329 2193-5807 2013/04 [Refereed][Not invited]
The addition reactions of diaryl disulfides (ArSSAr) to alkenes and alkynes were achieved with a catalytic amount of an arylbis(arylthio)sulfonium ion (ArS(ArSSAr)(+)), which was generated and accumulated by low-temperature electrolysis of ArSSAr, to give the corresponding diarylthiolated products. The electrolysis of a mixture of ArSSAr and an alkene with a catalytic amount of electricity was also effective to drive the reactions. A cation chain mechanism mediated by ArS(ArSSAr)(+) as a chain carrier is suggested. - Reaction Integration Using Electrochemically Generated Cationic SpeciesYosuke AshikariKyoto University 2013 [Refereed][Not invited]
- Yosuke Ashikari, Toshiki Nokami, Jun-ichi YoshidaORGANIC & BIOMOLECULAR CHEMISTRY 11 (20) 3322 - 3331 1477-0520 2013 [Refereed][Not invited]
An integration of electrooxidative cyclization and chemical oxidation was achieved. Electrochemical oxidation of alkenes having a nucleophilic moiety in the presence of DMSO gave cyclized alkoxysulfonium ions, which were converted to the corresponding ketones by treatment with triethylamine in a one-pot sequential manner. The method is also an effective tool for cyclization of 1,6-dienes affording five-membered ring diketones in high stereoselectivity. - Kouichi Matsumoto, Yuki Kozuki, Yosuke Ashikari, Seiji Suga, Shigenori Kashimura, Jun-ichi YoshidaTETRAHEDRON LETTERS 53 (15) 1916 - 1919 0040-4039 2012/04 [Refereed][Not invited]
Arylbis(arylthio)sulfonium ions (ArS(ArSSAr)(+)), which were generated and accumulated by the low-temperature electrolysis of diary! disulfide (ArSSAr), were found to serve as ArS+ equivalent in electrophilic substitution reactions of aromatic compounds, enolizable ketones, enol acetates, ketene silyl acetals and allylsilanes to give the corresponding arylthiolated products. (C) 2012 Elsevier Ltd. All rights reserved. - Yosuke Ashikari, Toshiki Nokami, Jun-ichi YoshidaORGANIC LETTERS 14 (3) 938 - 941 1523-7060 2012/02 [Refereed][Not invited]
Oxidative hydroxylation of toluene derivatives via alkoxysulfonium ion intermediates was achieved by integration of anodic oxidation and hydrolysis to give benzyl alcohols which are also susceptible to oxidation. Alkenes were also oxidized to give 1,2-diols without overoxidation. The integration of electrochemical oxidative cyclization and hydrolysis was achieved using alkenes bearing a nitrogen atom in an appropriate position to give cyclic beta-amino-substituted alcohols. - Yosuke Ashikari, Toshiki Nokami, Jun-ichi YoshidaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133 (31) 11840 - 11843 0002-7863 2011/08 [Refereed][Not invited]
Generation of carbocations by the "cation pool" method followed by reaction with dimethyl sulfoxide (DMSO) gave the corresponding alkoxysulfonium ions. Alkoxysulfonium ions could also be generated by in situ DMSO trapping of electrochemically generated carbocations. The resulting alkoxysulfonium ions were transformed into carbonyl compounds by treatment with triethylamine. The present integrated electrochemical chemical oxidation can be applied to the oxidation of diarylmethanes to diaryl ketones, toluenes to benzaldehydes, and aryl-substituted alkenes to 1,2-diketones. Moreover, the oxidation of unsaturated compounds bearing a nucleophilic group in an appropriate position gives cyclized carbonyl compounds. - Seiji Suga, Ikuo Shimizu, Yosuke Ashikari, Yusuke Mizuno, Tomokazu Maruyama, Jun-ichi YoshidaCHEMISTRY LETTERS 37 (9) 1008 - 1009 0366-7022 2008/09 [Refereed][Not invited]
Electro-initiated coupling reactions of N-acyliminium 1011 with arylthiomethylsilanes and aryloxymethylsilanes were developed. Pulse electrolyses with intervals were found to be quite effective for the initiation. A chain mechanism involving cation, radical cation, and radical intermediates has been proposed.
MISC
- University of Washington での研究生活芦刈洋祐 OMNews 2023- (3) 102 -103 2023/08 [Not refereed][Invited]
- 藤井明子, 山田強, 小川綾, 増田快音, 寺西航, 朴貴煥, 芦刈洋祐, 富安範行, 市川智大, 宮本利一, 白鴻志, 松山清, 松山清, 永木愛一郎, 佐治木弘尚 日本病院薬剤師会東海ブロック・日本薬学会東海支部合同学術大会講演要旨集 2020- 2020
Books etc
- リビング重合技術 高度な制御を可能にする精密重合と応用展開早乙女広樹, 芦刈洋祐, 永木愛一郎 (Contributorリビング重合の制御性向上に寄与するフローマイクロリアクターシステム)
2024/10 (ISBN: 9784864283229) - 月刊ファインケミカル2024年7月号「フロー・マイクロ合成―次世代合成の最前線―」芦刈洋祐, 永木愛一郎 (ContributorAIを活用したフロー化学研究)
2024/07 - 実験の自動化・自律化によるR&Dの効率化と運用方法芦刈洋祐, 玉木孝, 永木愛一郎 (ContributorAI技術を用いたフロー自動合成と実験の短縮)
技術情報協会 2023/12 (ISBN: 9784861049941) - Enabling Tools and Techniques for Organic Synthesis: A Practical Guide to Experimentation, Automation, and ComputationYosuke Ashikari, Aiichiro Nagaki (ContributorIntroduction to Flow Chemistry for the Synthetic Chemist)
Willy 2023/10 (ISBN: 9781119855637) - フローマイクロ合成の最新動向芦刈洋祐, 永木愛一郎 (Contributor高分子合成反応)
シーエムシー出版 2021/08 - 芦刈洋祐、永木愛一郎 (Contributorマイクロチャネル：マイクロ混合・反応)
マイクロ・ナノ熱工学の進展編集委員会 2021/05 (ISBN: 9784860437220) 6, 10, 731, 17p, 図版 [38] p - フロー合成、連続生産のプロセス設計、条件設定と応用事例前川圭, 芦刈洋祐, 永木愛一郎 (Contributorフローリアクターを用いた鈴木－宮浦カップリング反応)
技術情報協会 2020/12 - フロー合成、連続生産のプロセス設計、条件設定と応用事例芦刈洋祐, 永木愛一郎 (Contributorフローリアクターを用いた不安定中間体を経由する反応集積化)
技術情報協会 2020/12 - フロー合成、連続生産のプロセス設計、条件設定と応用事例芦刈洋祐, 永木愛一郎 (Contributorフローマイクロリアクターの高速混合を利用した高選択的化学反応)
技術情報協会 2020/12 - マイクロリアクター/フロー合成による 反応条件を最適化した導入と目的に応じた実生産への適用 ～事例をふまえた現状と課題 / 不具合を避けるための設備設計～芦刈 洋祐, 永木 愛一郎 (Contributor有機合成への応用技術と実用化事例)
サイエンス＆テクノロジー 2020/04
Presentations
- Regioselective Electrocatalytic Deuteration Reactions in PEM ReactorYosuke Ashikari, Yiyue Yao, Masahiro Takumi, Aiichiro NagakiPacific Rim Meeting on Electrochemical and Solid State Science 2024 (PRiME2024) 2024/10
- 重合活性種のインライン分析に基づくメタクリレート類のフローマイクロアニオン重合 [Not invited]芦刈洋祐, 吉岡里佳子, 米倉裕哉, 劉東垠, 岡本和紘, 永木愛一郎第73回高分子討論会 2024/09
- 高反応性化学種の自在制御を志向したフローマイクロ合成化学 [Invited]芦刈洋祐鳥取大学講演会 2024/09
- 高速フロー電解セルを用いたO-Cグリコシド転位反応の開発 [Not invited]芦刈洋祐, 姚弋越, 宅見正浩, 永木愛一郎第48回有機電子移動化学討論会 2024/06
- 高速電解フロー法を基軸とするO-Cグリコシド転位反応の速度研究および合成応用 [Not invited]姚弋越, 芦刈洋祐, 宅見正浩, 永木愛一郎日本化学会第104年会 2024/03
- Flash Synthetic Chemistry Guided by Flow Microreactor Research [Invited]Yosuke Ashikari3rd International Conference on Automated Flow and Microreactor Synthesis (ICAMS-3) 2023/12
- フローマイクロリアクターを活用した高速反応制御およびデータ駆動型研究開発 [Invited]芦刈洋祐第101回フロー・マイクロ合成研究会 2023/11
- プロトン交換膜型電解リアクターを用いた重水素導入法の開発と機械学習による条件最適化 [Not invited]芦刈洋祐, 姚弋越, 萬代恭子, 玉木孝, 永木愛一郎第47回有機電子移動化学討論会 2023/06
- フローマイクロリアクターを用いたバイメタリックアレーンの合成と非対称ビアリール合成への展開 [Not invited]芦刈洋祐, 川口倫子, 永木愛一郎日本農芸化学会2023年度大会 2023/03
- 高速マイクロ混合に基づくタンパク質の水中化学修飾の研究 [Invited]芦刈洋祐公益財団法人中外創薬科学財団令和4年度助成研究報告会 2023/03
- アニオン重合の実用化を志向したフロー精密重合の実証 [Invited]芦刈洋祐HSFC Demo Day 2023/02
- アニオン性マスク法に基づくバイメタリックアレーンのフローマイクロ合成 [Not invited]芦刈洋祐, 永木愛一郎化学系学協会北海道支部2023年冬季研究発表会 2023/01
- フローマイクロリアクターにより合成したバイメタリックアレーン類の化学選択的カップリング反応 [Not invited]芦刈洋祐, 川口倫子, 萬代恭子, 相澤瑤子, 永木愛一郎日本化学会第101春季年会 2021/03
- Generation and Reactions of Aryllithiums via Highly-Coordinated Anionic Intermediates Using Flow Microreactors [Not invited]Yosuke ASHIKARI, Daisuke ICHINARI, Kyoko MANDAI, Yoko AIZAWA, Jun-ichi YOSHIDA, Aiichiro NAGAKI日本化学会第100春季年会 2020/03
- 電解発生有機硫黄カチオン種を利用した重合性アルケンのオキソチオレーション [Not invited]芦刈洋祐, 齊藤巧泰, 野上敏材, 吉田潤一, 永木愛一郎日本化学会第100春季年会 2020/03
- Masked Azide Strategy: Functionalization of Organic Azides via Generation and Reactions of Organolithiums using Flow Microreactors [Invited]Yosuke Ashikari, Daisuke Ichinari, Yoko Aizawa, Kyoko Mandai, Jun-ichi Yoshida, Aiichiro NagakiThe 18th Asian Chemical Congress (18ACC) 2019/12
- Oxo-thiolation of Cationically Polymerizable Alkenes with Anodic Cations Using Flow Microreactors [Not invited]Yosuke Ashikari, Kodai Saito, Toshiki Nokami, Jun-ichi Yoshida, Aiichiro NagakiThe 12th International Symposium on Integrated Synthesis (ISONIS-12) 2019/11
Association Memberships
Research Projects
- 日本学術振興会：科学研究費助成事業Date (from‐to) : 2024/04 -2027/03Author : 芦刈 洋祐
- 日本学術振興会：科学研究費助成事業 国際共同研究加速基金(国際共同研究強化(B))Date (from‐to) : 2020/10 -2026/03Author : 永木 愛一郎, 宮村 浩之, 信田 尚毅, 殿村 修, 芦刈 洋祐有機カチオン種は正電荷を有した短寿命な活性中間体であり、化学反応や生体反応において最も頻繁に発生する中間体の一つである。有機化学分野で古くから合成に利用されており、現在も主にカチオン前駆体とLewis酸から求核剤が共存する条件においてカチオン中間体を平衡的（可逆的）に発生させ、求核剤で瞬時に補足することにより様々な化合物合成に利用されている。一方で、有機カチオン種は、その不安定さから求核剤の共存しない条件（非共存条件）において非平衡的（不可逆的）に発生させることは困難であり、これがカチオン化学の展開を妨げてきた。特に糖鎖合成の中心となるグリコシル化反応の鍵中間体と考えられているグリコシルカチオンは、極めて不安定であることから、直接的な観測は達成されておらず、その構造や反応性の研究は推定の域を出ていない。このような背景のもと、本国際共同研究では、フランスポワティエ大学のThibaudeau教授との共同研究を通し、我々のフローマイクロ合成技術とThibaudearu教授の超強酸技術とを融合させた超強酸フロー技術の構築を行う。本年度は、フローマイクロリアクターを用いた不可逆的なグリコシルカチオン発生を目指し、高速電解合成が可能なフロー型電解合成装置の開発を行った。その結果、グリコシルカチオンと同種の構造を有する環状オキソニウムカチオンの発生と反応をフロー反応により達成できた。次年度は本装置を活用し、グリコシルカチオンのフローリアクターによる発生に挑戦したい。
- フローマイクロ技術による生体高分子の高精度ケミカルコンジュゲーションの研究公益財団法人高橋産業経済研究財団：令和6年度研究助成金援助事業Date (from‐to) : 2024/04 -2026/03
- 不安定カチオン種の発生・反応および分析を可能とする電気化学反応装置の開発研究補助事業公益財団法人JKA：2024年度自転車等機械振興事業に関する補助金Date (from‐to) : 2024/04 -2026/03
- 重水素化機能材料の創生を志向した電解フローリアクターの開発公益財団法人JKA：2023年度自転車等機械振興事業に関する補助金Date (from‐to) : 2023/04 -2024/03Author : 芦刈洋祐
- Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research Grant-in-Aid for Early-Career ScientistsDate (from‐to) : 2020/04 -2023/03Author : 芦刈 洋祐不安定活性種を不可逆的に発生可能な有機電解反応において、従来不可能であった、炭素カチオンなどの不安定活性種の合成利用を実現すべく研究を行った。特に寿命が1秒に満たないような極めて不安定な炭素カチオンなどの活性種を短時間で発生できるフローマイクロ電解装置を開発し、その高次利用を基軸とした、複数の活性種を経由する新規分子変換反応の開発を目指して研究を行った。本年度は、昨年度に引き続き電極の材質を最適化するとともに、電解反応デバイス自体の改良を行った。その結果、バッチ型電解装置ではほとんど生成物の得られない、オキソニウムカチオンの発生とその求核剤との反応を高効率的に行うことができた。さらにこれまで検討してきた小スケール合成に加えて、生産を志向した大スケール合成の検討を行った。すなわち不安定中間体の一種であるイミニウムカチオンの発生と反応において、長時間の送液が可能な送液装置を活用し、60分間の連続反応を行うことにより、生理活性物質の前駆体をグラムスケールで合成することに成功した。これは、装置および反応システムの頑健性を示すものであり、大スケール生産や合成の工業化に展開可能であることを示す結果である。今後は、極めて不安定でありながら合成価値の高い活性種であるグリコシルカチオンおよびその類縁体に注力し、その発生と合成利用を可能とするフローマイクロ電解装置および電解技術の開発とその実現に挑戦していく。
- 公益財団法人北海道科学技術総合振興センター：大学発新産業創出プログラム(START) 大学・エコシステム推進型 起業活動支援プログラム研究開発課題Date (from‐to) : 2022/10 -2023/02Author : 芦刈洋祐
- 多種金属置換基を有する芳香族化合物合成法の確立とそのカップリング反応の開拓京都技術科学センター：2021年度研究開発助成Date (from‐to) : 2021/04 -2022/03Author : 芦刈洋祐
- Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C)Date (from‐to) : 2016/04 -2019/03Author : Nuriya Mutsuo, ASHIKARI Yosuke, MIZUGUCHI TakahaIn this study, we investigated the structure-function relationship of astrocytes, non-neuronal cells whose roles in brain physiology and pathophysiology have been recently realized. We revealed that various proteins that were located at the microstructures of astrocytes were dynamically regulated by drugs and biological molecules that had been considered to exert their functions through their actions on neurons. Furthermore, we have also succeeded in developing and applying microscopy methods that are effective in investigating astrocyte functions. Future studies based on these progresses are expected to reveal the structure function relationship of astrocytes and its roles in physiology and pathophysiology of the brain.
Industrial Property Rights
- 特開2023-165103:シークエンスオリゴマー及びポリマー並びにその製造方法 2023/11/15永木 愛一郎, 芦刈 洋祐, 北山 健司 国立大学法人京都大学, 株式会社ダイセル
- 特開2023-078733:白金族元素担持多孔性粒子及び白金族元素触媒、並びにこれらが充填されたカラム 2023/06/07永木 愛一郎, 前川 圭, 芦刈 洋祐, 石塚 紀生, 松山 清 株式会社ａｌｔＦｌｏｗ, 株式会社エマオス京都
- 特願2021-032262:ポリマーの製造方法、並びにハロゲン化スチレン類モノマー重合用開始剤、及びその製造方法 2021年/03永木愛一郎, 石川進, 高橋裕輔, 芦刈洋祐, 古澤真維, 米倉裕哉, 玉木孝 国立大学法人京都大学, 東邦化学工業株式会社
- 特願2020-214198:モノ重水素化ジハロゲン化メタン、重水素化シクロプロパン化合物及びそれらの製造方法 2020年/12/23永木愛一郎, 芦刈洋祐, 土橋祐太 国立大学法人京都大学, 大陽日酸株式会社
- 特開2018-144488:Additive Manufacturing Using Stimuli-Responsive High-Performance Polymers 2018/09/20Lee. C.-U, Goetz, A. E, Ashikari, Y, Boydston, A. J, Ganter, M. A, Storti, D. W リコー、ユニヴァーシティオブワイントン
- 特願2020-535822:化合物、化合物の塩、神経機能調節物質、神経機能調節物質の評価方法、化合物の製造方法、及び化合物の塩の製造方法 2018年/08/07塗谷睦生, 芦刈洋祐, 藤本ゆかり, 安井正人 学校法人慶應義塾