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Generations and Reactions of Reactive Organic Cations Using Flow Redox Systems

Research Project

Project/Area Number 15350056
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

SUGA Seiji  Kyoto University, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (50291430)

Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥15,300,000 (Direct Cost: ¥15,300,000)
Fiscal Year 2005: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2004: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2003: ¥7,900,000 (Direct Cost: ¥7,900,000)
Keywordsflow system / redox system / carbocation / electron-transfer reaction / electrochemical micro flow cell / carbon-carbon bond formation / 反応活性炭素種 / カチオンプール法 / カチオンフロー法 / 電解セル / 酸化還元反応 / カルバメート / 酸化 / 還元 / 炭素ラジカル / アルコキカルベニウムイオン / アジルイミニウムイオン / 電解酸化 / フロー型マイクロ電解セル / 炭素求核剤 / N-アシルイミニウムイオン / 液相コンビナトリアル合成
Research Abstract

Recently we have developed the "cation pool" method, which involves generation of highly reactive carbocations by low temperature electrolysis followed by reactions with a variety of nucleophiles. Micro flow reactors have received significant interest in the stream of downsizing of chemistry, and they are expected to make an innovative and revolutionary change for chemical synthesis. The advantages of microflow reactors of easy modulation and the possibility of combining reactors are quite useful to construct flow type redox systems for the organic transformations. On the basis of this concept we have developed "cation flow" method using microflow electrochemical reactors, which involves generation of highly reactive carbocations by low temperature electrolysis. This method enables the manipulation of carbocation intermediates to achieve direct oxidative C-C bond formation. Based on the "cation flow" method, continuous sequential combinatorial synthesis can be accomplished by simple flow switching. As an extension of the "cation flow" method, an electrochemical paired micro flow system that involves concurrent anodic generation of carbocations and cathodic generation of carbon nucleophiles followed by their reactions to achieve straightforward C-C bond formation has been developed. Anodic methoxylation of several organic compounds have also been achieved in the absence of intentionally added supporting electrolyte using an electrochemical microflow system.

Report

(4 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (48 results)

All 2005 2004 2003 Other

All Journal Article (40 results) Book (6 results) Publications (2 results)

  • [Journal Article] Microflow Electroorganic Synthesis without Supporting Electrolyte.2005

    • Author(s)
      Horcajada, R., Okajima, M., Suga, S., Yoshida, J.
    • Journal Title

      Chem. Commun.

      Pages: 1303-1305

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Enhancement of Chemical Selectivity by Microreactors.2005

    • Author(s)
      Yoshida, J., Nagaki, A., Iwasaki, T., Suga, S
    • Journal Title

      Chem. Eng. Technol. 28

      Pages: 259-266

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] "Cation pool" method based on C-C bond dissociation. Effective generation of monocations and dications.2005

    • Author(s)
      Okajima, M., Suga, S., Itami, K., Yoshida, J.
    • Journal Title

      J. Am. Chem. Soc 127

      Pages: 6930-6931

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Radical Addition to "Cation Pool". Reverse Process of Radical Cation Fragmentation.2005

    • Author(s)
      Maruyama, T., Suga, S., Yoshida, J.
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 7324-7325

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Cycloaddition of "N-Acyliminium Ion Pools" with Carbon-Carbon Multiple Bonds.2005

    • Author(s)
      Suga, S., Tsutsui, Y., Nagaki, A., Yoshida, J.
    • Journal Title

      Bull. Chem. Soc. Jpn 78

      Pages: 1206-1217

    • NAID

      10016579889

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electrochemical Combinatorial Organic Syntheses Using Micro Flow Systems.2005

    • Author(s)
      Suga, S., Okajima, M., Fujiwara, K., Yoshida, J.
    • Journal Title

      QSAR Comb. Sci. 24

      Pages: 728-741

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Control of Extremely Fast Competitive Consecutive Reactions Using Micromixing. Selective Friedel-Crafts Aminoalkylation.2005

    • Author(s)
      Nagaki, A., Togai, M., Suga, S., Aoki, N., Mae, K., Yoshida, J.
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 11666-11675

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Intramolecular Participation in Alkoxycarbenium Ion Pools.2005

    • Author(s)
      Suga, S., Suzuki, S., Yoshida, J.
    • Journal Title

      Org. Lett. 6

      Pages: 4717-4720

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] マイクロリアクターを用いた選択的有機反応2005

    • Author(s)
      吉田潤一, 菅 誠治, 永木愛一郎
    • Journal Title

      有機合成化学協会誌 63・5

      Pages: 511-522

    • NAID

      10015727437

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Microflow Electroorganic Synthesis without Supporting Electrolyte.2005

    • Author(s)
      Horcajada, R., Okajima, M., Suga, S., Yoshida, J.
    • Journal Title

      Chem.Commun.

      Pages: 1303-1305

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Enhancement of Chemical Selectivity by Microreactors.2005

    • Author(s)
      Yoshida, J., Nagaki, A., Iwasaki, T., Suga, S.
    • Journal Title

      Chem.Eng.Technol. 28

      Pages: 259-266

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] "Cation pool" method based on C-C bond dissociation. Effective generation of monocations and dications.2005

    • Author(s)
      Okajima, M., Suga, S., Itami, K., Yoshida, J.
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 6930-6931

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Radical Addition to "Cation Pool". Reverse Process of Radical Cation Fragmentation.2005

    • Author(s)
      Maruyama, T., Suga, S., Yoshida, J.
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 7324-7325

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Cycloaddition of "N-Acyliminium Ion Pools" with Carbon-Carbon Multiple Bonds.2005

    • Author(s)
      Suga, S., Tsutsui, Y., Nagaki, A., Yoshida, J.
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 1206-1217

    • NAID

      10016579889

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electrochemical Combinatorial Organic Syntheses Using Micro Flow Systems.2005

    • Author(s)
      Suga, S., Okajima, M., Fujiwara, K., Yoshida, J.
    • Journal Title

      QSAR Comb.Sci. 24

      Pages: 728-741

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Control of Extremely Fast Competitive Consecutive Reactions Using Micromixing. Selective Friedel-Crafts Aminoalkylation.2005

    • Author(s)
      Nagaki, A., Togai, M., Suga, S., Aoki, N., Mae, K., Yoshida, J
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 11666-11675

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Intramolecular Participation in Alkoxycarbenium Ion Pools.2005

    • Author(s)
      Suga, S., Suzuki, S., Yoshida, J.
    • Journal Title

      Org.Lett. 6

      Pages: 4717-4720

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] "Cation pool"method based on C-C bond dissociation. Effective generation of monocations and dications.2005

    • Author(s)
      Okajima, M., Suga, S., Itami, K., Yoshida, J.
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 6930-6931

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Radical Addition to"Cation Pool". Reverse Process of Radical Cation Fragmentation.2005

    • Author(s)
      Maruyama, T., Suga, S., Yoshida, J.
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 7324-7325

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Cycloaddition of"N-Acyliminium Ion Pools"with Carbon-Carbon Multiple Bonds.2005

    • Author(s)
      Suga, S., Tsutsui, Y., Nagaki, A., Yoshida, J.
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 1206-1217

    • NAID

      10016579889

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Control of Extremely Fast Competitive Consecutive Reactions Using Micromixing. Selective Friedel-Crafts Aminoalkylation.2005

    • Author(s)
      Nagaki, A., Togai, M., Suga, S., Aoki, N., Mae, K., Yoshida, J.
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 11666-11675

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Generation of Carbon Free Radicals by the Reduction of Cation Pool.2004

    • Author(s)
      Suga, S., Suzuki, S., Maruyama, T., Yoshida, J.
    • Journal Title

      Bull. Chem. Soc. Jpn. 77

      Pages: 1545-1554

    • NAID

      10013451778

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Cationic Carbohydroxylation of Alkenes and Alkynes Using the Cation Pool Method.2004

    • Author(s)
      Suga, S., Kageyama, Y., Babu, G., Itami, K., Yoshida, J.
    • Journal Title

      Org. Lett. 6

      Pages: 2709-2711

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Generation of Alkoxycarbenium Ion Pools from Thioacetals and Applications to Glycosylation Chemistry.2004

    • Author(s)
      Suzuki, S., Matsumoto, K., Kawamura, K., Suga, S., Yoshida, J.
    • Journal Title

      Org. Lett. 6

      Pages: 3755-3758

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Three-Component Coupling Based on the "Cation Pool" Method.2004

    • Author(s)
      Suga, S., Nishida, T., Yamada, D., Nagaki, A., Yoshida, J.
    • Journal Title

      J. Am. Chem. Soc. 126

      Pages: 14702-14703

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] "Cation Pool" Initiated Controlled/Living Polymerization Using Microsystems.2004

    • Author(s)
      Nagaki, A., Kawamura, K., Suga, S., Ando, T., Sawamoto, M., Yoshida
    • Journal Title

      J. J. Am. Chem. Soc. 126

      Pages: 14338-14339

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Generation of Carbon Free Radicals by the Reduction of Cation Pool2004

    • Author(s)
      Suga, S., Suzuki, S., Maruyama, T., Yoshida, J.
    • Journal Title

      Bull.Chem.Soc.Jpn. 77

      Pages: 1545-1554

    • NAID

      10013451778

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Cationic Carbohydroxylation of Alkenes and Alkynes Using the Cation Pool Method.2004

    • Author(s)
      Suga, S., Kageyama, Y., Babu, G., Itami, K., Yoshida, J.
    • Journal Title

      Org.Lett. 6

      Pages: 2709-2711

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Generation of Alkoxycarbenium Ion Pools from Thioacetals and Applications to Glycosylation Chemistry2004

    • Author(s)
      Suzuki, S., Matsumoto, K., Kawamura, K., Suga, S., Yoshida, J.
    • Journal Title

      Org.Lett. 6

      Pages: 3755-3758

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Three-Component Coupling Based on the "Cation Pool" Method.2004

    • Author(s)
      Suga, S., Nishida, T., Yamada, D., Nagaki, A., Yoshida, J.
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 14702-14703

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] "Cation Pool" Initiated Controlled/Living Polymerization Using Microsystems.2004

    • Author(s)
      Nagaki, A., Kawamura, K., Suga, S., Ando, T., Sawamoto, M., Yoshida, J
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 14338-14339

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Generation of Carbon Free Radicals by the Reduction of Cation Pool2004

    • Author(s)
      Suga, S., Suzuki, S., Maruyama, T., Yoshida, I.
    • Journal Title

      Bull.Chem.Soc.Jpn. 77

      Pages: 1545-1554

    • NAID

      10013451778

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Cationic Carbohydroxylation of Alkenes and Alkynes Using the Cation Pool Method2004

    • Author(s)
      Suga, S., Kageyama, Y., Babu, G., Itami, K., Yoshida, I.
    • Journal Title

      Org.Lett. 6

      Pages: 2709-2711

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Generation of Alkoxycarbenium Ion Pools from Thioacetals and Applications to Glveosvlation Chemistry2004

    • Author(s)
      Suzuki, S., Matsumoto, K., Kawamura, K., Suga, S., Yoshida, I.
    • Journal Title

      Org.Lett. 6

      Pages: 3755-3758

    • Related Report
      2004 Annual Research Report
  • [Journal Article] "Cation Pool"Initiated Controlled/Living Polymerization Using Microsystems.2004

    • Author(s)
      Nagaki, A., Kawamura, K., Suga, S., Ando, T., Sawamoto, M., Yoshida, J.
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 14338-14339

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Three-Component Coupling Based on the "Cation Pool"Method.2004

    • Author(s)
      Suga, S., Nishida, T., Yamada, D., Nagaki, A., Yoshida, J.
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 14702-14703

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Highly Selective Friedel-Crafts Monoalkylation Using Micromixing2003

    • Author(s)
      Suga, S., Nagaki, A., Yoshida, J.
    • Journal Title

      Chem. Commun.

      Pages: 354-355

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] "N-Acyliminium Ion Pool" as a Hetero Diene in [4+2] Cycloaddition Reaction.2003

    • Author(s)
      Suga, S., Nagaki, A., Tsutsui, Y., Yoshida, J.
    • Journal Title

      Org. Lett. 5

      Pages: 945-947

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Highly Selective Friedel-Crafts Monoalkylation Using Micromixing.2003

    • Author(s)
      Suga, S., Nagaki, A., Yoshida, J.
    • Journal Title

      Chem.Commun.

      Pages: 354-355

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] "N-Acyliminium Ion Pool" as a Hetero Diene in [4+2] Cycloaddition Reaction.2003

    • Author(s)
      Suga, S., Nagaki, A., Tsutsui, Y., Yoshida, J.
    • Journal Title

      Org.Lett. 5

      Pages: 945-947

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Book] マイクロリアクターテクノロジー "マイクロリアクターによる選択的有機合成"2005

    • Author(s)
      菅 誠治
    • Publisher
      エヌ・ティー・エス
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Book] 有機電解合成の新展開 "カチオンプール法およびカチオンフロー法による有機電解合成"2004

    • Author(s)
      吉田潤一, 菅 誠治
    • Publisher
      シーエムシー出版
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Book] マイクロ化学チップの技術と応用 "合成システム"2004

    • Author(s)
      吉田潤一, 菅 誠治
    • Publisher
      丸善
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Book] ロボット・マイクロ合成最前線 "マイクロリアクターを用いた選択的有機合成反応"2004

    • Author(s)
      菅 誠治, 吉田潤一
    • Publisher
      化学同人
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Book] 有機電融合成の新展開"カチオンプール法およびカチオンフロー法による有機電解合成"2004

    • Author(s)
      吉田潤一, 菅 誠治
    • Total Pages
      12
    • Publisher
      シーエムシー出版
    • Related Report
      2004 Annual Research Report
  • [Book] 実験化学講座 基礎編IV "有機電解"2003

    • Author(s)
      菅 誠治
    • Publisher
      丸善
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Publications] Suga, S., Nagaki, A., Yoshida, J.: "Highly Selective Friedel-Crafts Monoalkylation Using Micromixing"Chem.Commun.. 354-355 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Suga, S., Nagaki, A., Tsutsui, Y., Yoshida, J.: ""N-Acyliminium Ion Pool" as a Hetero Diene in [4+2] Cycloaddition Reaction"Org.Lett.. 5. 945-947 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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