Development of catalytic introduction of heteroatom-based functional groups via the cleavage of carbon-heteroatom bonds

• Project/Area Number: 18H01978
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Osaka University
• Principal Investigator: Tobisu Mamoru 大阪大学, 工学研究科, 教授 (60403143)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000); Fiscal Year 2020: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2019: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2018: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
• Keywords: 炭素ーヘテロ原子結合切断 / 有機リン化合物 / 有機硫黄化合物 / 遷移金属触媒 / 異性化 / フッ素化 / 有機合成 / 触媒反応 / ヘテロ原子 / 有機ホウ素化合物

Outline of Final Research Achievements

Catalytic reactions that involve the cleavage of a carbon-heteroatom bond were examined, in particular, focusing on those through the formation of onium salts. This led to the development of nickel-catalyzed synthesis of phospholes from bisphosphines via the double cleavage of carbon-phosphorus bonds. A similar transformation using the corresponding sulfur analogs was found to be catalyzed by a thiolate base. Intermolecular annulation between triarylphosphines and arynes to form phosphole derivatives via the cleavage of a carbon-phosphorus bond was also developed.

Academic Significance and Societal Importance of the Research Achievements

Ｃ－Ｈ結合の活性化を基盤とする研究が激増する中、炭素－ヘテロ原子結合の活性化に着目した研究は少ない。さらに、そのアプローチとして、「触媒的なオニウム塩形成」が一般性のあるアプローチであることを実証できた。これらの成果は、取り扱いに難のある反応性ヘテロ原子導入試薬を使わずに、安定な３級ホスフィンやスルフィドをリンや硫黄源とする有機合成を可能にする。硫黄、リンといったヘテロ官能基は分子の機能発現に決定的な役割を果たすため、これらの官能基を自在に導入する新手法の開発は、それらの機能性分子のより環境調和型の供給に資する。

Research Products

• [Journal Article] Phosphine-Catalyzed Intermolecular Acylfluorination of Alkynes via a P(V) Intermediate (2020)
  • Author(s): Fujimoto Hayato、Kodama Takuya、Yamanaka Masahiro、Tobisu Mamoru
  • Journal Title: Journal of the American Chemical Society Volume: 142 Issue: 41 Pages: 17323-17328
  • DOI: 10.1021/jacs.0c08928
  • Peer Reviewed
• [Journal Article] The Effect of the Leaving Group in N-Heterocyclic Carbene-Catalyzed Nucleophilic Aromatic Substitution Reactions (2020)
  • Author(s): Kosuke Yasui, Miharu Kamitani, Hayato Fujimoto, and Mamoru Tobisu
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 93 Issue: 12 Pages: 1424-1429
  • DOI: 10.1246/bcsj.20200210
  • NAID: 130007955885
  • Peer Reviewed
• [Journal Article] Aryne-Induced SNAr/Dearylation Strategy for the Synthesis of Fluorinated Dibenzophospholes from Triarylphosphines via a P(V) Intermediate (2020)
  • Author(s): Fujimoto Hayato、Kusano Momoka、Kodama Takuya、Tobisu Mamoru
  • Journal Title: Organic Letters Volume: 22 Issue: 6 Pages: 2293-2297
  • DOI: 10.1021/acs.orglett.0c00489
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed B-Diarylation of Diethylaminoborane for the Synthesis of Diarylborinic Acids (2020)
  • Author(s): Ryoma Shimazumi, Takuya Igarashi, and Mamoru Tobisu
  • Journal Title: Chem. Lett. Volume: 49 Issue: 7 Pages: 760-763
  • DOI: 10.1246/cl.200213
  • NAID: 130007872522
  • Peer Reviewed
• [Journal Article] Thiolate-Initiated Synthesis of Dibenzothiophenes from 2,2′-Bis(methylthio)-1,1′-Biaryl Derivatives through Cleavage of Two Carbon-Sulfur Bonds (2019)
  • Author(s): Masuya Yoshihiro、Kawashima Yuki、Kodama Takuya、Chatani Naoto、Tobisu Mamoru
  • Journal Title: Synlett Volume: 30 Issue: 17 Pages: 1995-1999
  • DOI: 10.1055/s-0037-1611974
  • Peer Reviewed
• [Journal Article] Cyclization of Bisphosphines to Phosphacycles via the Cleavage of Two Carbon-Phosphorus Bonds by Nickel Catalysis (2019)
  • Author(s): Fujimoto Hayato、Kusano Momoka、Kodama Takuya、Tobisu Mamoru
  • Journal Title: Organic Letters Volume: 21 Issue: 11 Pages: 4177-4181
  • DOI: 10.1021/acs.orglett.9b01355
  • Peer Reviewed