Direct Transformation from Benzene to Pentacene: Development of Synthetic Method for Pentacenes via Tetracycle Formation

• Project/Area Number: 18K19083
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 33:Organic chemistry and related fields
• Research Institution: Osaka Metropolitan University (2022); Osaka City University (2018-2021)
• Principal Investigator: Satoh Tetsuya 大阪公立大学, 大学院理学研究科, 教授 (40273586)
• Project Period (FY): 2018-06-29 – 2023-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000); Fiscal Year 2020: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2018: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
• Keywords: パイ共役分子 / カルボン酸 / 脱水素カップリング / ロジウム触媒 / アントラセン / 縮合環形成 / ベンゾチオフェン / 酸化剤フリー / 酸化的カップリング / 還元的カップリング / 環形成 / 遷移金属触媒 / カップリング / 環化

Outline of Final Research Achievements

The purpose of this study is to develop new methods for synthesizing functional pi-conjugated molecules including condensed heterocycles from readily available starting materials in a short step by using the transition-metal-catalyzed intermolecular coupling of aromatic substrates. Consequently, we succeeded in constructing a series of fused (hetero)aromatic compounds with diverse skeletons and structures.

Academic Significance and Societal Importance of the Research Achievements

縮合（ヘテロ）芳香環骨格は、有機エレクトロニクスとして利用される機能性有機分子や天然物中に見られることから、その合成法の開発は社会的にも注目されている。本研究では、そのような骨格を簡便に直接的に構築する手法の開発に成功している。一例として、ロジウム触媒存在下、3-（アセチルアミノ）クマリン類をアルキンとともに反応させると、脱水素および脱アセチル化を伴う連続ダブルC-H環化が起こり、五環式縮合ピロール誘導体が一段階で合成できることを見出した。得られた五環式構造は、様々な生物活性を示す天然海洋アルカロイドのラメラリン類のものと類似することから、その特性についても興味が持たれる。

Research Products

• [Journal Article] Ligand-Dependant Selective Synthesis of Mono- and Dialkenylcarbazoles through Rhodium(III)-Catalyzed C-H Alkenylation (2023)
  • Author(s): Rikuto Tanaka, Shiho Ochiai, Asumi Sakai, Yoshinosuke Usuki, Bubwoong Kang, Tetsuro Shinada, Tetsuya Satoh
  • Journal Title: Chem. Asian J. Volume: 18 Issue: 4
  • DOI: 10.1002/asia.202201210
  • Peer Reviewed / Open Access
• [Journal Article] Construction of Thienopyrroles through Rhodium-Catalyzed Direct Annulation of (Acetylamino)thiophenes with Alkynes (2023)
  • Author(s): Mikishiro Hayashi, Ryudai Michikita, Yoshinosuke Usuki, Tetsuya Satoh
  • Journal Title: Synthesis Volume: 55 Issue: 21 Pages: 3582-3588
  • DOI: 10.1055/a-2015-4466
  • Peer Reviewed / Open Access
• [Journal Article] Rhodium-Catalyzed Annulative Coupling of Coumarin-3-Carboxylic Acids with Alkynes (2023)
  • Author(s): Mikishiro Hayashi, Kengo Komori, Yoshinosuke Usuki, Tetsuya Satoh
  • Journal Title: Chem. Lett. Volume: 52 Issue: 5 Pages: 307-309
  • DOI: 10.1246/cl.230082
  • Peer Reviewed
• [Journal Article] Construction of Pyrrolocoumarin Cores through Double C−H Annulation Cascade (2022)
  • Author(s): Ryudai Michikita, Yoshinosuke Usuki, Tetsuya Satoh
  • Journal Title: Eur. J. Org. Chem. Volume: 2022 Issue: 22 Pages: E202200550
  • DOI: 10.1002/ejoc.202200550
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019839
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of Benzylidenesuccinates through Rhodium(III)-Catalyzed C-H Alkenylation with Itaconate (2022)
  • Author(s): Ochiai Shiho, Yoshimoto Risa, Usuki Yoshinosuke, Satoh Tetsuya
  • Journal Title: Asian Journal of Organic Chemistry Volume: 11 Issue: 2 Pages: e202100774
  • DOI: 10.1002/ajoc.202100774
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019658
  • 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
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019657
  • 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
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2020502
  • Peer Reviewed / Open Access
• [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
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019751
  • 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 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] 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
  • NAID: 120006998406
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019737
  • Peer Reviewed / Open Access
• [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: 48 Issue: 5 Pages: 461-464
  • DOI: 10.1246/cl.190024
  • NAID: 130007642580
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019744
  • 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] 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
  • NAID: 120006936888
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019598
  • Peer Reviewed / Open Access
• [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
  • NAID: 120006783765
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2020134
  • Peer Reviewed
• [Journal Article] Rhodium(III)-Catalyzed Annulative Carbon-Hydrogen Bond Functionalization (2019)
  • Author(s): Satoh Tetsuya、Miura Masahiro
  • Journal Title: Rhodium Catalysis in Organic Synthesis: Methods and Reactions Volume: - Pages: 487-519
  • DOI: 10.1002/9783527811908.ch18
  • Int'l Joint Research
• [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: 24 Issue: 31 Pages: 7852-7855
  • DOI: 10.1002/chem.201801245
  • NAID: 120006649311
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2019730
  • 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
  • NAID: 120006773393
  • URL: https://ocu-omu.repo.nii.ac.jp/records/2020008
  • Peer Reviewed
• [Journal Article] Theoretical Investigation of Regioselectivity in the Rh-Catalyzed Coupling Reaction of 3-Phenylthiophene with Styrene (2018)
  • Author(s): HAYASHI Yoshihiro、SATOH Tetsuya、MIURA Masahiro、KAWAUCHI Susumu
  • Journal Title: Journal of Computer Chemistry, Japan Volume: 17 Issue: 5 Pages: 217-218
  • DOI: 10.2477/jccj.2018-0063
  • NAID: 130007608155
  • ISSN: 1347-1767, 1347-3824
  • Peer Reviewed
• [Presentation] ロジウム触媒を用いたN-アセチルアミノチオフェ ン類とアルキンの脱水素カップリング反応 (2023)
  • Author(s): 林幹史朗，臼杵克之助，佐藤哲也
  • Organizer: 日本化学会第103 春季年会
• [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 (2022)
  • 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] ロジウム触媒を用いるN-アシルカルバゾール類の直接的C-Hアルケニル化反応 (2022)
  • Author(s): 田中陸人，落合紫帆，酒井明日実，臼杵克之助，姜法雄、品田哲郎、佐藤哲也
  • Organizer: 日本化学会第102 春季年会
• [Presentation] ロジウム触媒を用いる分子内C-H/O-Hカップリングによる芳香族ラクトン誘導体の合成 (2022)
  • Author(s): 西田彩子，稲井康仁，臼杵克之助，佐藤哲也
  • Organizer: 日本化学会第102 春季年会
• [Presentation] ロジウム触媒による炭素-水素結合切断を経るN-アシルカルバゾール類のモノおよびジアルケニル化 (2022)
  • Author(s): 田中陸人，臼杵克之助，姜法雄、品田哲郎、佐藤哲也
  • Organizer: 第68 回有機金属化学討論会
• [Presentation] 芳香族ラクトン誘導体の合成を指向したロジウム触媒C-H/O-H カップリングの開発 (2022)
  • Author(s): 西田彩子，稲井康仁，臼杵克之助，佐藤哲也
  • Organizer: 第68 回有機金属化学討論会
• [Presentation] アミドを配向基とするパラジウム触媒を用いたα-ア ミノ酸のβ位C(sp3)-H アセトキシ化反応 (2022)
  • Author(s): 松村篤志，臼杵克之助，佐藤哲也
  • Organizer: 錯体化学会第72 回討論会
• [Presentation] ロジウム(III)錯体触媒を用いるN-アシルカルバゾールの直接アルケニル化: 配位子による反応制御 (2022)
  • Author(s): 田中陸人，落合紫帆，酒井明日実，臼杵克之助，姜法雄、品田哲郎、佐藤哲也
  • Organizer: 錯体化学会第72 回討論会
• [Presentation] クロスカップリング入門 (2021)
  • Author(s): 佐藤哲也
  • Organizer: 大阪市立大学化学セミナー
  • Invited
• [Presentation] 遷移金属触媒を用いる新規カップリング反応の開発 (2021)
  • Author(s): 佐藤哲也
  • Organizer: 第41回有機合成若手セミナー「明日の有機合成を担う人のために」
  • Invited
• [Presentation] Rhodium(III)- and Iridium(III)-Catalyzed Dehydrogenative Coupling of Aromatic Substrates with Unsaturated Compounds (2021)
  • Author(s): Tetsuya Satoh
  • Organizer: 104th Canadian Chemistry Conference and Exhibition (IUPAC | CCCE 2021)
  • Int'l Joint Research / Invited
• [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] Iridium-Catalyzed Dehydrogenative and Decarboxylative Coupling of Salicylic Acids with Internal Alkynes (2019)
  • Author(s): Tetsuya Satoh
  • Organizer: 4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research
• [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] Synthesis of Fused Heterocycles via Transition Metal-Catalyzed C-H Functionalization, In Handbook of CH-Functionalization (2022)
  • Author(s): Yoshinosuke Usuki, Tetsuya Satoh / Debabrata Maiti Ed.
  • Total Pages: 18
  • Publisher: Wiley-VCH
  • ISBN: 9783527834242
• [Book] Handbook of CH-Functionalization (2022)
  • Author(s): Yoshinosuke Usuki, Tetsuya Satoh
  • Publisher: Wiley-VCH
• [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: 12
  • Publisher: シーエムシー出版
  • ISBN: 9784781314211