Generations and Reactions of Reactive Organic Cations Using Flow Redox Systems

• Project/Area Number: 15350056
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: KYOTO 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: ¥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)
• Keywords: flow 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.

Research Products

• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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(欧文)」より
• [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
• [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(欧文)」より
• [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
• [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
• [Journal Article] Generation of Carbon Free Radicals by the Reduction of Cation Pool (2004)
  • Author(s): Suga, S., Suzuki, S., Maruyama, T., Yoshida, I.
  • Journal Title: Bull.Chem.Soc.Jpn. 77 Pages: 1545-1554
  • NAID: 10013451778
• [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, I.
  • Journal Title: Org.Lett. 6 Pages: 2709-2711
• [Journal Article] Generation of Alkoxycarbenium Ion Pools from Thioacetals and Applications to Glveosvlation Chemistry (2004)
  • Author(s): Suzuki, S., Matsumoto, K., Kawamura, K., Suga, S., Yoshida, I.
  • Journal Title: Org.Lett. 6 Pages: 3755-3758
• [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
• [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
• [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(和文)」より
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [Publications] Suga, S., Nagaki, A., Yoshida, J.: "Highly Selective Friedel-Crafts Monoalkylation Using Micromixing"Chem.Commun.. 354-355 (2003)
• [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)