Development of Unique Condensed Aromatic Compounds Using Ring-closing Approach

• Project/Area Number: 18K05097
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Chiba University
• Principal Investigator: Yoshida Kazuhiro 千葉大学, 大学院理学研究院, 准教授 (60375607)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: 有機合成 / 面不斉 / 閉環 / 芳香族化合物 / 含窒素複素環芳香族化合物

Outline of Final Research Achievements

Modern synthetic organic chemistry has sufficient flexibility to construct acyclic compounds selectively. Therefore, the construction of aromatic rings from acyclic precursors is an attractive approach to obtain substituted aromatic compounds without the formation of inseparable regioisomers. In this study, we have tried to synthesize some unique condensed aromatic compounds using such ring-closing approach. Specifically, we conducted research on the following issues. 1) Practical synthesis and application of asymmetric pyridine catalysts, 2) Synthesis of 4-quinolones, 3) Synthesis of [1]benzothiopheno[2,3-b][1]benzothiphene derivatives.

Academic Significance and Societal Importance of the Research Achievements

芳香族化合物を合成する上で現在欠かすことのできない役割を担っているのが、芳香族求電子置換反応である。しかし、多種多様な芳香族化合物の需要が高まりつつある中、芳香族求電子置換反応だけでは合成することが困難な芳香族化合物が多数存在する。本研究は、人類社会の発展に寄与すべく、置換基をあらかじめ望みの位置に配置した鎖状化合物から芳香環自体を構築するという我々がこれまで独自に開発してきた芳香族化合物合成法を大幅に発展させることを目指して実施した研究である。

Research Products

• [Journal Article] Enantioselective Desymmetrization of 1,3‐Disubstituted Adamantane Derivatives via Rhodium‐Catalyzed C-H Bond Amination: Access to Optically Active Amino Acids Containing Adamantane Core (2021)
  • Author(s): Yasue Risa、Yoshida Kazuhiro
  • Journal Title: Advanced Synthesis & Catalysis Volume: 363 Issue: 6 Pages: 1662-1671
  • DOI: 10.1002/adsc.202001419
  • Peer Reviewed
• [Journal Article] <i>N</i>-Heterocyclic Carbene Ligands Having Planar Chiral Ferrocene Structure (2020)
  • Author(s): Yoshida Kazuhiro、Yasue Risa
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 78 Issue: 1 Pages: 28-40
  • DOI: 10.5059/yukigoseikyokaishi.78.28
  • NAID: 130007783804
  • ISSN: 0037-9980, 1883-6526
  • Year and Date: 2020-01-01
  • Peer Reviewed
• [Journal Article] Oxidative Cyclization ofo-(1-Hydroxy-2-alkynyl)-N-tosylanilides for the Synthesis of 4-Quinolones (2020)
  • Author(s): Ueda Jun-ichi、Enomoto Yuuki、Seki Mizuki、Konishi Takuma、Ogasawara Masamichi、Yoshida Kazuhiro
  • Journal Title: The Journal of Organic Chemistry Volume: 85 Issue: 10 Pages: 6420-6428
  • DOI: 10.1021/acs.joc.0c00245
  • Peer Reviewed
• [Journal Article] Synthesis of [1]benzothiopheno[2,3-b][1]benzothiophene derivatives through iodine-mediated sulfuration reaction of 1,1-diarylethylenes (2020)
  • Author(s): Sakai Shuta、Sato Kazuki、Yoshida Kazuhiro
  • Journal Title: Tetrahedron Letters Volume: 61 Issue: 6 Pages: 151476-151476
  • DOI: 10.1016/j.tetlet.2019.151476
  • Peer Reviewed
• [Journal Article] Development of Planar Chiral Five-Membered Cyclic (Amino)(ferrocenylene)carbene Ligand and Its Iridium Dicarbonyl Complex (2020)
  • Author(s): Takagaki Waka、Yasue Risa、Yoshida Kazuhiro
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 93 Issue: 2 Pages: 200-204
  • DOI: 10.1246/bcsj.20190325
  • NAID: 130007798365
  • Peer Reviewed
• [Journal Article] Synthesis and Application of Planar Chiral Cyclic (Amino)(ferrocenyl)carbene Ligands Bearing FeCp* Group (2019)
  • Author(s): Yasue Risa、Yoshida Kazuhiro
  • Journal Title: Organometallics Volume: 38 Issue: 9 Pages: 2211-2217
  • DOI: 10.1021/acs.organomet.9b00171
  • Peer Reviewed
• [Journal Article] Chiral Bicyclic NHC/Cu Complexes for Catalytic Asymmetric Borylation of α,β-Unsaturated Esters (2019)
  • Author(s): Miwa Yuya、Kamimura Takumi、Sato Kiyoaki、Shishido Daichi、Yoshida Kazuhiro
  • Journal Title: The Journal of Organic Chemistry Volume: 84 Issue: 21 Pages: 14291-14296
  • DOI: 10.1021/acs.joc.9b02096
  • Peer Reviewed
• [Journal Article] Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis (2019)
  • Author(s): Yoshida Kazuhiro、Liu Qiang、Yasue Risa、Wada Shiro、Kimura Ryosuke、Konishi Takuma、Ogasawara Masamichi
  • Journal Title: ACS Catalysis Volume: 10 Issue: 1 Pages: 292-301
  • DOI: 10.1021/acscatal.9b04438
  • NAID: 120006937693
  • Peer Reviewed
• [Journal Article] Cover Feature: Planar‐Chiral Ferrocene‐Based N‐Heterocyclic Carbene Ligands (Chem. Eur. J. 70/2018) (2018)
  • Author(s): Yoshida Kazuhiro、Yasue Risa
  • Journal Title: Chemistry A European Journal Volume: 24 Issue: 70 Pages: 18565-18565
  • DOI: 10.1002/chem.201805458
• [Journal Article] Planar‐Chiral Ferrocene‐Based N‐Heterocyclic Carbene Ligands (2018)
  • Author(s): Yoshida Kazuhiro、Yasue Risa
  • Journal Title: Chemistry A European Journal Volume: 24 Issue: 70 Pages: 18575-18586
  • DOI: 10.1002/chem.201803903
  • Peer Reviewed
• [Presentation] ヨウ素アニオンを活用する分子内環化反応 (2020)
  • Author(s): 関 瑞希
  • Organizer: 千葉大学グローバルプロミネント研究基幹シンポジウム
• [Presentation] Synthesis and Application of Planar Chiral Cyclic(amino)(ferrocenyl)carbene Bearing Cp* Group (2019)
  • Author(s): Yasue Risa、Yoshida Kazuhiro
  • Organizer: 20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 20)
  • Int'l Joint Research
• [Presentation] Versatile and Enantiolselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis (2019)
  • Author(s): Yoshida Kazuhiro、Liu Qiang、Yasue Risa、Wada Shiro、Kimura Ryosuke、Konishi Takuma、Ogasawara Masamichi
  • Organizer: 4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research
• [Presentation] Synthesis and Application of Planar Chiral Cyclic(amino)(ferrocenyl)carbene Ligands Bearing FeCp* (2019)
  • Author(s): Yasue Risa、Yoshida Kazuhiro
  • Organizer: 4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research
• [Presentation] Planar Chiral Cyclic Amino(ferrocenyl)carbene as Ligand for Transition Metals (2018)
  • Author(s): Risa Yasue, Yuta Shikata, Kazuhiro Yoshida
  • Organizer: Symposium on Molecular Chirality 2018
• [Presentation] 面性不斉五員環アミノフェロセニルカルベン配位子の開発 (2018)
  • Author(s): 高垣 和果、安江 里紗、四方 祐太、吉田 和弘
  • Organizer: 第75回有機合成化学協会関東支部シンポジウム
• [Presentation] フェロセン縮環した面不斉環状ホスホン酸類の不斉合成 (2018)
  • Author(s): 劉 強、安江 里紗、岡崎 願之晋、吉田 和弘、小笠原 正道
  • Organizer: 第65回有機金属化学討論会
• [Presentation] Fe(C5Me5)基をもつ新規面性不斉NHC配位子の開発 (2018)
  • Author(s): 安江 里紗、四方 祐太、吉田 和弘
  • Organizer: 第65回有機金属化学討論会
• [Presentation] Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis (2018)
  • Author(s): Kazuhiro Yoshida, Qiang Liu, Risa Yasue, Shiro Wada, Ryosuke Kimura, Masamichi Ogasawara
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry
  • Int'l Joint Research
• [Presentation] Development of Planar Chiral (Amino)(ferrocenyl)carbene Ligand Having Cp*Fe Moiety (2018)
  • Author(s): Risa Yasue, Yuta Shikata, Kazuhiro Yoshida
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry
  • Int'l Joint Research