Development of Novel Electron-Transfer Reactions via Organonitrogen Active Species

• Project/Area Number: 17K05861
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Kyoto University
• Principal Investigator: Okamoto Kazuhiro 京都大学, 工学研究科, 助教 (30552658)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2019: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2017: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: 有機活性種 / 遷移金属触媒 / 電子移動 / コバルト触媒 / 含窒素複素環 / 不斉合成 / 触媒的不斉合成 / 一電子移動 / 鉄触媒 / オキシムエステル / ラジカル / 含窒素化合物 / 均一系触媒 / 酸化還元

Outline of Final Research Achievements

We have developed transition metal-catalyzed transformation of cyclic O-acyloximes as an novel type of precursors for organonitrogen active species. In this study, we have utilized 3d transition metal catalysts such as iron and cobalt for such transformations. As a result, we have developed cobalt- and iron-catalyzed several types of transformation reactions of O-acyloximes into various nitrogen-containing heterocyclic molecules.

Academic Significance and Societal Importance of the Research Achievements

本研究成果は電子移動型反応による有機窒素活性種の新規発生法開発という当初目的を十分に達成したと言える．電子移動型反応は効率に優れた反応であるため，様々な触媒反応の効率化に果たす役割は大きく，この成果が有機合成化学の発展を含む分子科学への貢献を将来的に果たすことが予想され，ひいては本邦の社会経済に対する将来的な貢献も期待される．

Research Products

• [Journal Article] Recent Progress on Cyclic Nitrenoid Precursors in Transition-metal-catalyzed Nitrene-transfer Reactions (2019)
  • Author(s): T. Shimbayashi, K. Sasakura, A. Eguchi, K. Okamoto, K. Ohe
  • Journal Title: Chem. Eur. J. Volume: 25 Issue: 13 Pages: 3156-3180
  • DOI: 10.1002/chem.201803716
  • Peer Reviewed
• [Journal Article] Facile Construction of Tetrahydropyrrolizines by Iron-Catalyzed Double Cyclization of Alkene-Tethered Oxime Esters with 1,2-Disubstituted Alkenes (2018)
  • Author(s): Shimbayashi Takuya，Nakamoto Daiki，Okamoto Kazuhiro，Ohe Kouichi
  • Journal Title: Organic Letters Volume: 印刷中 Issue: 10 Pages: 3044-3048
  • DOI: 10.1021/acs.orglett.8b01073
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Selective Formation of Substituted Pyrroles from Alkene-tethered Cyclic Oxime Esters (2018)
  • Author(s): Kazuhiro Okamoto, Tomohiro Oda, Gaku Matsushita, Takuya Shimbayashi, Kohei Sasakura, and Kouichi Ohe
  • Journal Title: Heterocycles Volume: 97 Issue: 1 Pages: 218-231
  • DOI: 10.3987/com-17-s(t)4
  • Peer Reviewed
• [Journal Article] Incorporation of Monatomic Cations onto an Ir-Ir Bond in a Dimeric Iridium(II) Complex Having a 1,3-Diene-1,4-diyl Backbone (2018)
  • Author(s): Kohei Sasakura, Kazuhiro Okamoto, and Kouichi Ohe
  • Journal Title: Organometallics Volume: 37 Issue: 14 Pages: 2319-2324
  • DOI: 10.1021/acs.organomet.8b00299
  • Peer Reviewed
• [Journal Article] Divergent Catalytic Approach from Cyclic Oxime Esters to Nitrogen-Containing Heterocycles with Group 9 Metal Catalysts (2018)
  • Author(s): Takuya Shimbayashi, Gaku Matsushita, Atsushi Nanya, Akira Eguchi, Kazuhiro Okamoto, and Kouichi Ohe
  • Journal Title: ACS Catalysis Volume: 8 Issue: 9 Pages: 7773-7780
  • DOI: 10.1021/acscatal.8b01646
  • Peer Reviewed
• [Journal Article] Iron-Catalyzed Aminative Cyclization/Intermolecular Homolytic Aromatic Substitution Using Oxime Esters and Simple Arenes (2018)
  • Author(s): Takuya Shimbayashi, Kazuhiro Okamoto, and Kouichi Ohe
  • Journal Title: Chemistry An Asian Journal Volume: 13 Issue: 4 Pages: 395-399
  • DOI: 10.1002/asia.201701634
  • Peer Reviewed
• [Journal Article] Copper-Catalyzed Regio- and Stereoselective Iodocyanation and Dicyanation of Alkynes with Cyanogen Iodide (2017)
  • Author(s): Naoki Sakata, Kohei Sasakura, Gaku Matsushita, Kazuhiro Okamoto and Kouichi Ohe
  • Journal Title: Organic Letters Volume: 19 Issue: 13 Pages: 3422-3425
  • DOI: 10.1021/acs.orglett.7b01378
  • Peer Reviewed
• [Journal Article] Radical-Polar-Crossover Reactions of Vinyl Boron-Ate Complexes (2017)
  • Author(s): Marvin Kischkewitz, Kazuhiro Okamoto, Christian Mueck-Lichtenfeld, and Armido Studer
  • Journal Title: Science Volume: 355 Issue: 6328 Pages: 936-938
  • DOI: 10.1126/science.aal3803
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Generation of Stable Ruthenium(IV)-Ketimido Complexes via Oxidative Addition of Oxime Esters to Ruthenium(II): Reactivity Studies Based on Electronic Properties of the Ru-N Bond (2017)
  • Author(s): Takuya Shimbayashi, Kazuhiro Okamoto, and Kouichi Ohe
  • Journal Title: Chemistry A European Journal Volume: 23 Issue: 66 Pages: 16892-16897
  • DOI: 10.1002/chem.201704102
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of 2H-Azirines with Tetrasubstituted Stereocenters by Enantioselective Ring-Contraction of Isoxazoles (2017)
  • Author(s): Kazuhiro Okamoto, Atsushi Nanya, Akira Eguhi, and Kouichi Ohe
  • Journal Title: Angewandte Chemie International Edition Volume: 57 Issue: 4 Pages: 1039-1043
  • DOI: 10.1002/anie.201710920
  • Peer Reviewed
• [Presentation] 双性イオン型白金(II)錯体を用いた触媒的 (2018)
  • Author(s): 岡本 和紘・渡辺 飛路・舩坂 怜司・笹倉 康平・ 末崎 雅大・大江 浩一
  • Organizer: 第６５回有機金属化学討論会
• [Presentation] 有機一電子酸化剤を用いた四級有機ボラートの炭素-炭素結合形成を伴う選択的リガンドカップリング反応 (2018)
  • Author(s): 中本 大貴・岡本 和紘・大江 浩一
  • Organizer: 日本化学会第98春季年会
• [Presentation] Construction of N-Heterocyclic Molecules via Transition Metal-Catalyzed N-O Bond Cleavage of Isoxazoles (2018)
  • Author(s): EGUCHI, Akira; SASAKI, Masumi; NANYA, Atsushi; OKAMOTO, Kazuhiro; OHE, Koichi
  • Organizer: 日本化学会第98春季年会
• [Presentation] Synthesis of Tetrahydropyrrolizine via Iron-Catalyzed Cycloaddition of Alkene-Tethered Oxime Esters with Michael Acceptors (2018)
  • Author(s): SHIMBAYASHI, Takuya; OKAMOTO, Kazuhiro; OHE, Kouichi
  • Organizer: 日本化学会第98春季年会
• [Presentation] コバルト触媒によるN,O-複素環のNーO結合切断をきっかけとするアザ二環式化合物の合成 (2018)
  • Author(s): 松下 岳・新林 卓也・岡本 和紘・大江 浩一
  • Organizer: 日本化学会第98春季年会
• [Presentation] ジシランを用いるアリル及びプロパルギルエーテルへの白金触媒によるシリレン挿入反応 (2018)
  • Author(s): 岡本 和紘・大月 直人・大江 浩一
  • Organizer: 日本化学会第98春季年会
• [Presentation] Transition Metal-Catalyzed Decarboxylative Reactions of Isoxazol-5(4H)-ones Affording Various Nitrogen-Containing Heterocycles (2017)
  • Author(s): Kazuhiro Okamoto
  • Organizer: International Symposium on Pure & Applied Chemistry (ISPAC) 2017
  • Int'l Joint Research / Invited
• [Presentation] Synthesis of Azabicyclic Compounds via Cobalt-Catalyzed N-O Bond Cleavage of N,O-Heterocycles (2017)
  • Author(s): 松下岳，新林卓也，岡本和紘，大江浩一
  • Organizer: 第６４回有機金属化学討論会
• [Presentation] Iron-catalyzed Aminofunctionalization of Unsaturated Carbon-Carbon Bonds Tethered to Oxime Esters (2017)
  • Author(s): 新林卓也，岡本和紘，大江浩一
  • Organizer: 第６４回有機金属化学討論会
• [Remarks] 大江研究室
  • URL: http://www.ehcc.kyoto-u.ac.jp/eh31/home/index-j.html
• [Remarks] 物質エネルギー化学専攻 Facebook