Development of Catalytic Transformation Methods of Carboxylic Acids on Porous Reaction Field

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 18H04267
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Osaka City University
• Principal Investigator: 佐藤 哲也 大阪市立大学, 大学院理学研究科, 教授 (40273586)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2019: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: カルボン酸 / ロジウム触媒 / C-H活性化 / 脱炭酸 / 遷移金属触媒 / 直接カップリング / 触媒的変換

Outline of Annual Research Achievements

芳香族カルボン酸、ヘテロ芳香族カルボン酸、ならびにα,β-不飽和カルボン酸類は、その化学的安定性のため取り扱いが容易であり、また入手しやすいため、有用分子の合成における重要なビルディングブロックとなっている。これらの分子中に含まれるカルボキシ基は、金属触媒の金属中心に適度に配位するため、配向基として機能し、近傍の炭素―水素結合を触媒的に修飾することが可能となる。これまでに我々は、ペンタメチルシクロペンタジエニルロジウム触媒および銅塩を酸化剤として用い、安息香酸類をアルキンとともに反応させると、オルト位の炭素―水素結合の切断を伴って脱水素カップリングが起こり、イソクマリン誘導体を与えることを報告している。
本研究の最終年度にあたる令和元年度には、多様なカルボン酸の直接変換について検討を行い、同様のロジウム触媒を用いる条件で、α-トリフルオロメチルアクリル酸類とベンズアミドとの反応を行うと、β位の炭素―水素結合切断を伴ってレドックスニュートラルなカップリングが進行し、オルト位がアルキル化されたベンズアミドが選択的に得られることを見出した。さらにこれらの基質の組み合わせを、電子不足の3価ロジウム錯体触媒を用いて反応させると、脱水素カップリングののちに分子内求核付加による環化が起こり、トリフルオロメチル基を有するイソインドリノン誘導体が選択的に合成できることが明らかになった。
また可視光照射下、セリウム触媒を用いる条件で、フェニル酢酸などの様々な構造を有するカルボン酸が分子状酸素と反応し、脱炭酸を伴う酸素化により、アルデヒドなどのカルボニル化合物へと変換されることを明らかにした。特に2-フェニル-および2-イソプロピル安息香酸の反応では、酸素化ののちに環化が起こり、対応するラクトンが得られた。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Synthesis of Substituted Indene Derivatives via Silver-Catalyzed Annulative 1:1 Coupling of Secondary Benzyl Alcohols with Alkynes (2021)
  • Author(s): H. Morisaka, K. Hirosawa, Y. Inai, Y. Usuki, T. Satoh
  • Journal Title: Chem. Lett. Volume: 50 Issue: 3 Pages: 456-458
  • DOI: 10.1246/cl.200846
  • NAID: 130007995521
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of Indenones through Rhodium(III)-Catalyzed [3+2] Annulation Utilizing Recyclable Carbazolyl Leaving Group (2021)
  • Author(s): S. Ochiai, A. Sakai, Y. Usuki, B. Kang, T. Shinada, T. Satoh
  • Journal Title: Chem. Lett. Volume: 50 Issue: 4 Pages: 585-588
  • DOI: 10.1246/cl.200884
  • NAID: 130008025747
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of 7-Phenylindole Derivatives through Rhodium-Catalyzed Dehydrogenative Coupling of 2-(Acetylamino)-1,1’-biphenyls with Alkynes (2021)
  • Author(s): R. Michikita, Y. Usuki, T. Satoh
  • Journal Title: Asian J. Org. Chem. Volume: 10 Issue: 4 Pages: 868-871
  • DOI: 10.1002/ajoc.202100071
  • Peer Reviewed / Open Access
• [Journal Article] A Theoretical Study of Product Selectivity in Rhodium- Catalyzed Oxidative Coupling Reaction Caused by the Solvation Effect (2021)
  • Author(s): M. Higashi, N. Shibata, S. Takeno, T. Satoh, M. Miura, H. Sato
  • Journal Title: Heterocycles Volume: 103 Issue: 2 Pages: 952-952
  • DOI: 10.3987/com-20-s(k)64
  • Peer Reviewed
• [Journal Article] Synthesis of Benzo-Fused Cyclic Compounds via Rhodium-Catalyzed Decarboxylative Coupling of Aromatic Carboxylic Acids with Alkynes (2021)
  • Author(s): Y. Inai, Y. Usuki, T. Satoh
  • Journal Title: Synthesis Volume: 53 Issue: 17 Pages: 3029-3036
  • DOI: 10.1055/a-1416-6997
  • Peer Reviewed / Open Access
• [Journal Article] Cerium(IV) Carboxylate Photocatalyst for Catalytic Radical Formation from Carboxylic Acids: Decarboxylative Oxygenation of Aliphatic Carboxylic Acids and Lactonization of Aromatic Carboxylic Acids (2020)
  • Author(s): Satoru Shirase, Sota Tamaki, Koichi Shinohara, Keishi Hirosawa, Hayato Tsurugi, Tetsuya Satoh, Kazushi Mashima
  • Journal Title: Journal of the American Chemical Society Volume: 142 Issue: 12 Pages: 5668-5675
  • DOI: 10.1021/jacs.9b12918
  • Peer Reviewed
• [Journal Article] N-Acylcarbazole as a Selective Transamidation Reagent (2020)
  • Author(s): B. Kang, Y. Yasuno, H. Okamura, A. Sakai, T. Satoh, M. Kuse, T. Shinada
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 93 Issue: 8 Pages: 993-999
  • DOI: 10.1246/bcsj.20200116
  • NAID: 130007888018
  • Peer Reviewed
• [Journal Article] Rhodium(III)‐Catalyzed Redox‐Neutral Coupling of α‐Trifluoromethylacrylic Acid with Benzamides through Directed C?H Bond Cleavage (2020)
  • Author(s): Yoshimoto Risa、Usuki Yoshinosuke、Satoh Tetsuya
  • Journal Title: Chemistry - An Asian Journal Volume: 15 Issue: 6 Pages: 802-806
  • DOI: 10.1002/asia.201901776
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of CF3-Containing Isoindolinone Derivatives through Rhodium-Catalyzed Oxidative Coupling of Benzamides with 2-Trifluoromethylacrylate (2020)
  • Author(s): R. Yoshimoto, H. Morisaka, Y. Usuki, Y. Shibata, K. Tanaka, T. Satoh
  • Journal Title: Chem. Lett. Volume: 49 Issue: 12 Pages: 1481-1483
  • DOI: 10.1246/cl.200609
  • NAID: 130007956021
  • Peer Reviewed / Open Access
• [Journal Article] Iridium(III)‐Catalyzed Dehydrogenative Coupling of Salicylic Acids with Alkynes: Synthesis of Highly Substituted 1‐Naphthol Derivatives (2019)
  • Author(s): Hirosawa Keishi、Usuki Yoshinosuke、Satoh Tetsuya
  • Journal Title: Advanced Synthesis & Catalysis Volume: 361 Issue: 22 Pages: 5253-5257
  • DOI: 10.1002/adsc.201900919
  • Peer Reviewed / Open Access
• [Journal Article] Theoretical Investigation of Regioselectivity in the Rh-Catalyzed Coupling Reaction of 3-Phenylthiophene with Styrene (2019)
  • Author(s): Hayashi Yoshihiro、Satoh Tetsuya、Miura Masahiro、Kawauchi Susumu
  • Journal Title: European Journal of Organic Chemistry Volume: 2019 Issue: 19 Pages: 2998-3004
  • DOI: 10.1002/ejoc.201900110
  • NAID: 130007608155
  • Peer Reviewed
• [Journal Article] Total Syntheses and Configuration Assignments of JBIR-06 and Related Depsipeptides (2019)
  • Author(s): Hamada Chie、Usuki Yoshinosuke、Takeuchi Daiki、Ogawa Hikaru、Abe Ryota、Satoh Tetsuya
  • Journal Title: Organic Letters Volume: 21 Issue: 4 Pages: 965-968
  • DOI: 10.1021/acs.orglett.8b03944
  • Peer Reviewed
• [Journal Article] Rhodium(III)-Catalyzed β-Arylation and -Alkenylation of α-Trifluoromethylacrylic Acid (2019)
  • Author(s): Yoshimoto Risa、Usuki Yoshinosuke、Satoh Tetsuya
  • Journal Title: Chemistry Letters Volume: 印刷中 Issue: 5 Pages: 461-464
  • DOI: 10.1246/cl.190024
  • NAID: 130007642580
  • Peer Reviewed / Open Access
• [Journal Article] Rhodium(III)-Catalyzed Oxidative Coupling of N-Phenylindole-3-carboxylic Acids with Alkenes and Alkynes via C4H and C2H/C2H Bond Cleavage (2018)
  • Author(s): Okada, T.; Sakai, A.; Hinoue, T.; Satoh, T.; Hayashi, Y.; Kawauchi, S.; Cahndrababunaidu, K.; Miura, M.
  • Journal Title: J. Org. Chem. Volume: 83 Issue: 10 Pages: 5639-5649
  • DOI: 10.1021/acs.joc.8b00638
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Iridium‐Catalyzed Aerobic Coupling of Salicylaldehydes with Alkynes: A Remarkable Switch of Oxacyclic Product (2018)
  • Author(s): Shintaro Yamane, Tomoaki Hinoue, Yoshinosuke Usuki, Masumi Itazaki, Hiroshi Nakazawa, Yoshihiro Hayashi, Susumu Kawauchi, Masahiro Miura, Tetsuya Satoh
  • Journal Title: Chemistry - An Europian Journal Volume: 印刷中 Issue: 31 Pages: 7852-7855
  • DOI: 10.1002/chem.201801245
  • NAID: 120006649311
  • Peer Reviewed / Open Access
• [Journal Article] Rhodium(III)-Catalyzed Direct Alkenylation of Benzothiophenes and Related Heterocycles with Alkynes (2018)
  • Author(s): Morita Tomohiro、Morisaka Hideaki、Satoh Tetsuya、Miura Masahiro
  • Journal Title: Asian Journal of Organic Chemistry Volume: 7 Issue: 7 Pages: 1330-1333
  • DOI: 10.1002/ajoc.201800235
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed peri-Selective Direct Alkenylation of 1-(Methylthio)naphthalene (2018)
  • Author(s): Shigeno Masanori、Nishii Yuji、Satoh Tetsuya、Miura Masahiro
  • Journal Title: Asian Journal of Organic Chemistry Volume: 7 Issue: 7 Pages: 1334-1337
  • DOI: 10.1002/ajoc.201800212
  • Peer Reviewed
• [Journal Article] Evaluation of Inhibitory Activities of UK-2A, an Antimycin-Type Antibiotic, and Its Synthetic Analogues against the Production of Anti-inflammatory Cytokine IL-4 (2018)
  • Author(s): Usuki Yoshinosuke、Ishii Saho、Ijiri Minako、Yoshida Ken-Ichi、Satoh Tetsuya、Horigome Satoru、Yoshida Izumi、Mishima Takashi、Fujita Ken-Ichi
  • Journal Title: Journal of Natural Products Volume: 81 Issue: 11 Pages: 2590-2594
  • DOI: 10.1021/acs.jnatprod.8b00559
  • Peer Reviewed
• [Presentation] 高性能触媒および高効率触媒反応開発・触媒作用機構解明研究拠点の構築 (2021)
  • Author(s): 佐藤哲也
  • Organizer: 複合先端研究機構プロジェクト研究成果報告会
  • Invited
• [Presentation] 触媒的脱水素カップリングの新展開 (2019)
  • Author(s): 佐藤哲也
  • Organizer: 山田科学振興財団2019年度研究交歓会
  • Invited
• [Presentation] Regioselective C-H Functionalization under Rhodium(III)-Catalysis (2018)
  • Author(s): Tetsuya Satoh
  • Organizer: The 4th International Symposium on C-H Activation (ISCHA4)
  • Int'l Joint Research / Invited
• [Presentation] Synthesis of pai-Conjugated Molecules via Transition-Metal-Catalyzed C-H Functionalization (2018)
  • Author(s): Tetsuya Satoh
  • Organizer: 9th OCARINA International Symposium
  • Int'l Joint Research / Invited
• [Presentation] 炭素―水素結合活性化を基軸とする高効率分子変換法の開発 (2018)
  • Author(s): 佐藤哲也
  • Organizer: 長瀬科学技術振興財団平成29年度研究成果発表会
  • Invited
• [Presentation] カルボン酸等の入手容易なビルディングブロックの触媒的変換反応 (2018)
  • Author(s): 佐藤哲也
  • Organizer: 新学術領域研究「精密制御反応場」第５回公開シンポジウム
  • Invited
• [Book] 直接的芳香族カップリング反応の設計と応用 (2019)
  • Author(s): 佐藤哲也
  • Total Pages: 13
  • Publisher: シーエムシー出版
  • ISBN: 9784781314211
• [Book] Rhodium Catalysis in Organic Synthesis: Methods and Reactions (2019)
  • Author(s): Satoh Tetsuya、Miura Masahiro
  • Total Pages: 32
  • Publisher: Wiley‐VCH
  • ISBN: 9783527343645