Redox Conversion of Organic Reactive Intermediates

2010 Fiscal Year Final Research Report

• Project/Area Number: 20245008
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: YOSHIDA Jun-ichi Kyoto University, 大学院・工学研究科, 教授 (30127170)
• Co-Investigator(Kenkyū-buntansha): NOKAMI Toshiki 京都大学, 大学院・工学研究科, 助教 (60402963)
• Project Period (FY): 2008 – 2010
• Keywords: 有機カチオン / 有機ラジカル / 有機アニオン / レドックス / 活性種

Research Abstract

Reduction of organic cations generated by the cation pool method and oxidation of organic anions generated by the anion flow method were studied. The resulting organic radical species could be effectively used for synthetic reactions. The results obtained in this study open new possibilities of redox conversion of organic reactive intermediates in organic synthesis.

Research Products

• [Journal Article] Asymmetric Carbolithiation of Conjugated Enynes : A Flow Microreactor Enables the Use of Configurationally Unstable Intermediates before They Epimerize (2011)
  • Author(s): Tomida, Y., Nagaki, A., Yoshida, J.
  • Journal Title: J.Am.Chem.Soc. 133 Pages: 3744-3747
  • Peer Reviewed
• [Journal Article] Glycosyl Sulfonium Ions as Storable Intermediates for Glycosylations (2011)
  • Author(s): Nokami, T., Nozaki, Y., Saigusa, Y., Shibuya, A., Manabe, S., Ito, Y., Yoshida, J.
  • Journal Title: Org.Lett. 13 Pages: 1544-1547
  • Peer Reviewed
• [Journal Article] Organic reactions mediated by electrochemically generated ArS^+ (2011)
  • Author(s): Matsumoto, K., Suga, S., Yoshida, J.
  • Journal Title: Org.Biomol.Chem. 9 Pages: 2586-2596
  • Peer Reviewed
• [Journal Article] Green and Sustainable Chemical Synthesis Using Flow Microreactors (2011)
  • Author(s): Yoshida, J., Kim, H., Nagaki, A.
  • Journal Title: Chem.Sus.Chem. 4 Pages: 331-340
  • Peer Reviewed
• [Journal Article] (2011)
  • Author(s): Nagaki, A., Miyazaki. A., Tomida, Y., Yoshida, J.
  • Journal Title: Chem.Eng.J. 167 Pages: 548-555
  • Peer Reviewed
• [Journal Article] Generation and Reactions of Oxiranyllithiums Using a Flow Microreactor (2010)
  • Author(s): Nagaki, A., Takizawa. E., Yoshida, J.
  • Journal Title: Chem.-Eur.J. 16 Pages: 14149-14158
  • Peer Reviewed
• [Journal Article] Synthesis of Polystyrenes - Poly(alkylmethacrylates) Block Copolymers via Anionic Polymerization Using an Integrated Flow Microreactor System (2010)
  • Author(s): Nagaki, A., Miyazaki, A., Yoshida, J.
  • Journal Title: Macromolecules 43 Pages: 8424-8429
  • Peer Reviewed
• [Journal Article] Cross-Coupling in a Flow Microreactor. Space Integration of Lithiation and Murahashi Coupling (2010)
  • Author(s): Nagaki, A., Kenmoku, A., Moriwaki, Y., Hayashi, A., Yoshida, J.
  • Journal Title: Angew.Chem., Int.Ed. 49 Pages: 7543-7547
  • Peer Reviewed
• [Journal Article] A Flow Microreactor System Enables Organolithium Reactions without Protecting Alkoxycarbonyl Groups (2010)
  • Author(s): Nagaki, A., Kim, H., Moriwaki, Y., Matsuo, C., Yoshida, J.
  • Journal Title: Chem.-Eur.J. 16 Pages: 11167-11177
  • Peer Reviewed
• [Journal Article] Controlled Polymerizations Using Microreactors (2010)
  • Author(s): Nagaki, A., Yoshida, J.
  • Journal Title: Kobunshi 59 Pages: 569-573
  • Peer Reviewed
• [Journal Article] Building Addressable Libraries as Platforms for Biological Assays by an Electrochemical Method (2010)
  • Author(s): Yoshida, J., Nagaki, A.
  • Journal Title: Angew.Chem., Int.Ed. 49 Pages: 3720-3722
  • Peer Reviewed
• [Journal Article] A new highlysterically demanding silyl (TEDAMS) group. Synthesis by multiple substitution of tris(diphenylmethyl)silane with diarylcarbenium ions. (2010)
  • Author(s): Terao, K., Watanabe, T., Suehiro, T., Nokami, T., Yoshida, J.
  • Journal Title: Tetrahedron Lett. 51 Pages: 4107-4109
  • Peer Reviewed
• [Journal Article] Addition of ArSSAr to Carbon-Carbon Multiple Bonds Using Electrochemistry (2010)
  • Author(s): Fujie, S., Matsumoto, K., Suga, S., Nokami, T., Yoshida, J.
  • Journal Title: Tetrahedron 66 Pages: 2823-2829
  • Peer Reviewed
• [Journal Article] Cationic Three-Component Coupling Invollving an Optically Active Enamine Derivative. From Time Integration To Space Integration of Reactions (2010)
  • Author(s): Suga, S., Yamada, D., Yoshida, J.
  • Journal Title: Chem.Lett. 39 Pages: 404
  • Peer Reviewed
• [Journal Article] Generation and Reaction of Cyano-Substituted Aryllithium Compounds Using Microreactors (2010)
  • Author(s): Nagaki, A., Kim, H., Usutani, H., Matsuo, C., Yoshida, J.
  • Journal Title: Org.Biomol.Chem.(Selected by the Editorial Board of Synfacts (Synfacts 2010, 582.)) 8 Pages: 1212
  • Peer Reviewed
• [Journal Article] Thiofluorination of Carbon-Carbon Multiple Bonds Using Electrochemically Generated ArS(ArSSAr)^+BF4^- (2009)
  • Author(s): Fujie, S., Matsumoto, K., Suga, S., Yoshida J.
  • Journal Title: Chem.Lett. 38 Pages: 1186
  • Peer Reviewed
• [Journal Article] Direct and Indirect Electrochemical Generation of Alkoxycarbenium Ion Pools from Thioacetals (2009)
  • Author(s): Matsumoto, K., Ueoka, K., Suzuki, S., Suga, S., Yoshida, J.
  • Journal Title: Tetrahedron 65 Pages: 10901-10907
  • Peer Reviewed
• [Journal Article] Nitro-Substituted Aryl Lithium Compounds in Microreactor Synthesis : Switch between Kinetic and Thermodynamic Control (2009)
  • Author(s): Nagaki, A., Kim, H., Yoshida, J.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 8063-8065
  • Peer Reviewed
• [Journal Article] N-Bus-aziridinyllithiums Using Microreactors (2009)
  • Author(s): Nagaki, A., Takizawa, E., Yoshida, J.
  • Journal Title: Chem.Lett. 38 Pages: 1060-1061
  • Peer Reviewed
• [Journal Article] マイクロリアクターを用いたアニオン重合の制御 (2009)
  • Author(s): Nagaki, A., Yoshida, J.
  • Journal Title: 「マイクロリアクターによる合成技術と工業生産」サイエンス&テクノロジー Pages: 147-159
  • Peer Reviewed
• [Journal Article] Carbolithiation of Conjugated Enynes with Aryllithiums in Microflow System and Applications to Synthesis of Allenylsilanes (2009)
  • Author(s): Tomida, Y., Nagaki, A., Yoshida, J.
  • Journal Title: Org.Lett. 11 Pages: 3614-3617
  • Peer Reviewed
• [Journal Article] Addition of ArSSAr to dienes via Intramolecular C-C bond formation initiated by a catalytic amount of ArS^+ (2009)
  • Author(s): Matsumoto, K., Fujie, S., Suga, S., Nokami, T., Yoshida, J.
  • Journal Title: Chem.Commun. Pages: 5448
  • Peer Reviewed
• [Journal Article] Microflow System Controlled Anionic Polymerization of MMA (2009)
  • Author(s): Nagaki, A., Tomida, Y., Miyazaki. A., Yoshida, J.
  • Journal Title: Macromolecule 42 Pages: 4384-4387
  • Peer Reviewed
• [Journal Article] マイクロフロー合成化学の魅力 -時間を空間で制御する新しい合成化学の創製- (2009)
  • Author(s): Yoshida, J., Nagaki, A.
  • Journal Title: 化学 64 Pages: 22-26
  • Peer Reviewed
• [Journal Article] Synthesis of Unsymmetrical Substituted Biaryls via Sequential Lithiation of Dibromobiaryls Using Integrated Microflow Systems. (2009)
  • Author(s): Nagaki, A., Takabayashi, N., Tomida, Y., Yoshida, J.
  • Journal Title: Beilstein J.Org.Chem. 5 Pages: 16
  • Peer Reviewed
• [Journal Article] Generation and Reactions of α-Silyl Oxiranyllithium Using Microflow System. (2009)
  • Author(s): Nagaki, A., Takizawa, E., Yoshida, J.
  • Journal Title: Chem.Lett. 38 Pages: 486-487
  • Peer Reviewed
• [Journal Article] Oxiranyl Anion Methodology Using Microflow Systems (2009)
  • Author(s): Nagaki, A., Takizawa, E., Yoshida, J.
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 1654-1655
  • Peer Reviewed
• [Journal Article] Generation of Diarylcarbenium Ion Pools via Electrochemical C-H bond Dissociation. (2009)
  • Author(s): Okajima, M., Soga, K., Watanabe, T., Terao, K., Nokami, T., Suga, S., Yoshida, J.
  • Journal Title: Bull.Chem.Soc.Jpn 82 Pages: 594-599
  • Peer Reviewed
• [Journal Article] α- and β-Glycosyl Sulfonium Ions ; Generation and Reactivity. (2009)
  • Author(s): Nokami, T., Shibuya, A., Manabe, S., Ito, Y., Yoshida, J.
  • Journal Title: Chem.-Eur.J. 15 Pages: 2252-2255
  • Peer Reviewed
• [Journal Article] Electro-initiated Coupling Reactions of N-Acyliminium Ion Pools with Arylthiomethylsilanes and Aryloxymethylsilanes (2008)
  • Author(s): Suga, S., Shimizu, I., Ashikari, Y., Mizuno, Y., Maruyama, T., Yoshida, J.
  • Journal Title: Chem.Lett. 37 Pages: 1008-1009
  • Peer Reviewed
• [Journal Article] Aryllithium Compounds Bearing Alkoxycarbonyl Groups. Generation and Reactions Using a Microflow System. (2008)
  • Author(s): Nagaki, A., Kim, H., Yoshida, J.
  • Journal Title: Angew.Chem., Int.Ed. 47 Pages: 7833
  • Peer Reviewed
• [Journal Article] Synthesis of Unsymmetrical Biaryls by Means of Mono-Selective Reaction of polyhaloarenes Using Integrated Microflow System. (2008)
  • Author(s): Nagaki, A., Takabayashi, N., Tomida, Y., Yoshida, J.
  • Journal Title: Org.Lett. 10 Pages: 3937
  • Peer Reviewed
• [Journal Article] Microflow System Controlled Anionic Polymerization of Styrenes. (2008)
  • Author(s): Nagaki, A., Tomida, Y., Yoshida, J.
  • Journal Title: Macromolecules 41 Pages: 6322-6330
  • Peer Reviewed
• [Journal Article] Iterative Molecular Assembly Based on the Cation Pool Method. Convergent Synthesis of Dendritic Molecules. (2008)
  • Author(s): Nokami, T., Ohata, K.;, Inoue, M., Tsuyama, H., Shibuya, A., Soga, K., Okajima, M., Suga, S., Yoshida, J.
  • Journal Title: J.Am.Chem.Soc. 130 Pages: 10864-10865
  • Peer Reviewed
• [Journal Article] Electrocchemical Conversion of Thioglycosides to Glycosyl Triflate. (2008)
  • Author(s): Nokami, T., Shibuya, A., Yoshida, J.
  • Journal Title: Trends in Glycoscience and Glycotechnology 20 Pages: 175-185
  • Peer Reviewed
• [Journal Article] Microflow System Controlled Carbocationic Polymerization of Vinyl Ethers (2008)
  • Author(s): Nagaki, A., Iwasaki, T., Kawamura, K., Yamada, D., Suga, S., Ando, T., Sawamoto, M., Yoshida, J.
  • Journal Title: Chem.Asian J. 3 Pages: 1558
  • Peer Reviewed
• [Journal Article] Oligosaccharide Synthesis based on a One-pot Electrochemical Glycosylation-Fmoc Deprotection Sequence. (2008)
  • Author(s): Nokami, T., Tsuyama, H., Shibuya, A., Nakatsutsumi, T., Yoshida, J.
  • Journal Title: Chem.Lett. 37 Pages: 942-943
  • Peer Reviewed
• [Journal Article] Modern Strategies in Electroorganic Synthesis (2008)
  • Author(s): Yoshida, J., Kataoka, K., Horcajada, R., Nagaki, A.
  • Journal Title: Chem.Rev. 108 Pages: 2265
  • Peer Reviewed
• [Journal Article] Flash Chemistry: Fast Chemical Synthesis by Using Microreactors. (2008)
  • Author(s): Yoshida, J., Nagaki, A., Yamada, T.
  • Journal Title: Chem.-Eur.J. 14 Pages: 7450
  • Peer Reviewed
• [Journal Article] Synthesis of Thiochromans Based on Indirect Cation Pool Method. (2008)
  • Author(s): Matsumoto, K., Ueoka, K., Fujie, S., Suga, S., Yoshida, J.
  • Journal Title: Heterocycles 76 Pages: 1103
  • Peer Reviewed
• [Journal Article] An Electroinitiated Cation Chain Reaction : Intramolecular Carbon-Carbon Bond Formation between Thioacetal and Olefin Groups. (2008)
  • Author(s): Matsumoto, K., Fujie, S., Ueoka, K., Suga, S., Yoshida, J.
  • Journal Title: Angew.Chem., Int.Ed. 47 Pages: 2506-2508
  • Peer Reviewed
• [Presentation] 電解酸化を利用したグリコシルスルホニウムイオンの発生・蓄積とグリコシル化反応 (2011)
  • Author(s): 野上敏材
  • Organizer: 電気化学会第78回大会
  • Place of Presentation: 横浜国立大学
  • Year and Date: 20110329-20110331
• [Presentation] Synthesis of dendronized polymers using dendritic diarylcarbeniun ion pools (2010)
  • Author(s): 野上敏材
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
  • Place of Presentation: Hawaii, U.S.A.
  • Year and Date: 20101215-20101220
• [Presentation] Flash Chemistry Fast Chemical Synthesis in Flow Microreactors. (2010)
  • Author(s): 吉田潤一
  • Organizer: The 14th InternationalConferenceon Miniaturized Systems for Chemistry and Life Sciences(Plenary)
  • Place of Presentation: Groningen, The Netherlands
  • Year and Date: 20101003-20101007
• [Presentation] Flash Chemistry Fast Chemical Synthesis in Flow Microreactors (2010)
  • Author(s): 吉田潤一
  • Organizer: Ischia Advanced School of Organic Chemistry Ischia Porto(Invited)
  • Place of Presentation: Napoli, Italy
  • Year and Date: 20100925-20100929
• [Presentation] Electrochemical Activation of Thioglycosides Using Bu_4NOTf as an Electrolyte for Analysis of Glycosylation Intermediates and Oligosaccharide Synthesis (2010)
  • Author(s): 野上敏材
  • Organizer: The 25^<th> International Carbohydrate Symposium (ICS-2010)
  • Place of Presentation: 東京
  • Year and Date: 20100801-20100806
• [Presentation] Synergy between Organic Electrochemistr and Flow Microreactor Chemistry (2010)
  • Author(s): 吉田潤一
  • Organizer: PacifiChem 2010, Green Electrochemistry(Invited)
  • Place of Presentation: Hawaii, U.S.A.
  • Year and Date: 2010-12-17
• [Presentation] Flash chemistry using flow microreactors (2010)
  • Author(s): 吉田潤一
  • Organizer: PacifiChem2010. Achieving Efficiency in Organic Reactions via Greener Processes and Practices(Invited)
  • Place of Presentation: Hawaii, U.S.A.
  • Year and Date: 2010-12-17
• [Presentation] Iterative Molecular Assembly Based on theCation-Pool Method (2010)
  • Author(s): 吉田潤一
  • Organizer: Convergent Synthesis of Dendritic Molecules First Symposium on Electrosynthesis(Invited)
  • Place of Presentation: Bonn, Germany
  • Year and Date: 2010-10-02
• [Presentation] ArS^+ Initiated Addition of ArSSAr to Dienes via Intramolecular C-C Bond Formation (2010)
  • Author(s): 吉田潤一
  • Organizer: 217^<th> ECS Meeting, Manuel M. Baizer Award Symposium on Organic Electrochemistry Vancouver
  • Place of Presentation: Canada
  • Year and Date: 2010-04-25
• [Presentation] 時間を空間で制御する合成化学 (2010)
  • Author(s): 吉田潤一
  • Organizer: 第10回GSCシンポジウム学術総合センター(Invited)
  • Place of Presentation: 一橋記念講堂
  • Year and Date: 2010-03-04
• [Presentation] フラッシュケミストリーフローマイクロリアクターを用いる超高速精密有機合成 (2010)
  • Author(s): 吉田潤一
  • Organizer: 社団法人日本粉体工業技術協会 平成21年度 第3回晶析分科会(Invited)
  • Place of Presentation: キャンパスプラザ京都
  • Year and Date: 2010-02-02
• [Presentation] Iterative Molecular Assembly Based on the Cation-Pool Method. ConvergentSynthesis of Dendritic Molecules. (2009)
  • Author(s): 吉田潤一
  • Organizer: The Sixth International Forum on Chemistry of Functional Organic Chemicals(Invited)
  • Place of Presentation: The University of Tokyo
  • Year and Date: 20091114-20091116
• [Presentation] フラッシュフローケミストリー ミクロ構造をもつフロー型反応器中での超高速反応を利用する有機合成 (2009)
  • Author(s): 吉田潤一
  • Organizer: 平成21年度有機合成化学北陸セミナー(Invited)
  • Place of Presentation: 富山観光ホテル
  • Year and Date: 20091009-20091010
• [Presentation] Flash Chemistry. The Concept and Some Applications (2009)
  • Author(s): 吉田潤一
  • Organizer: The German Environment Foundation (DBU) Workshop Nobel Process Windowsin Chemical Engineering(Invited)
  • Place of Presentation: Osnabruck, Muenster Germany
  • Year and Date: 2009-12-10
• [Presentation] フラッシュフローケミストリー ミクロ構造をもつフロー型反応器中での超高速反応を利用する有機合成 (2009)
  • Author(s): 吉田潤一
  • Organizer: 有機合成化学協会関西支部幹事講演会
  • Place of Presentation: 塩野義製薬 摂津事業所
  • Year and Date: 2009-08-05
• [Presentation] フラッシュケミストリー マイクロリアクターを用いる高速化学合成」 (2009)
  • Author(s): 吉田潤一
  • Organizer: 九州大学先導研講演会
  • Place of Presentation: 九州大学先導研
  • Year and Date: 2009-07-05
• [Presentation] Flash Chemistry: Fast Chemical Synthesis in Micro Flow Systems (2008)
  • Author(s): 吉田潤一
  • Organizer: EuCheMS Chemistry Congress(Invited)
  • Place of Presentation: Torino Italy
  • Year and Date: 20080916-20080920
• [Presentation] Flash Chemistry: Fast Chemical Synthesis in Micro Flow Systems (2008)
  • Author(s): 吉田潤一
  • Organizer: Post ISOR2008
  • Place of Presentation: Taipei, Taiwan
  • Year and Date: 2008-11-24
• [Presentation] Iterative Molecular Assembly based on the Cation-PoolMethod. Convergent Synthesis of Dendritic Molecules (2008)
  • Author(s): 吉田潤一
  • Organizer: The 9th ISOR-2008(Invited)
  • Place of Presentation: Chaiyi, Taiwan
  • Year and Date: 2008-11-02
• [Book] Handbook of micro reactors : Devices, Reactions and Applications.lume 2 (Liquid Phase and Liquid/Liquid Phase Reactions : Addition and elimination reactions) (2009)
  • Author(s): Yoshida, J., Nagaki, A.
  • Publisher: Wiley-VCH
• [Book] Handbook of micro reactors : Devices, Reactions and Applications. Volume 2 (Liquid Phase and Liquid/Liquid Phase Reactions : Oxidations and reductions) (2009)
  • Author(s): Yoshida, J., Nagaki, A.
  • Publisher: Wiley-VCH
• [Book] Handbook of micro reactors : Devices, Reactions and Applications. Volume 2 (Gas Phase and Gas/Liquid Phase Reactions : Substitution) (2009)
  • Author(s): Yoshida, J., Nagaki, A.
  • Publisher: Wiley-VCH
• [Book] Handbook of micro reactors : Devices, Reactions and Applications. Volume 2 (Polymerization : Cationic Living Polymeriation) (2009)
  • Author(s): Yoshida, J., Nagaki, A.
  • Publisher: Wiley-VCH
• [Book] FLASH CHEMISTRY : Fast Organic Synthesis in Microsystems (2008)
  • Author(s): Yoshida, J.
  • Publisher: Wiley
• [Remarks] ホームページ等