Development of Hybrid Photocatalytic Reaction Systems for Aerobic Oxygenation of Hydrocarbons

• Project Area: Hybrid Catalysis for Enabling Molecular Synthesis on Demand
• Project/Area Number: 18H04650
• 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 University
• Principal Investigator: 大久保 敬 大阪大学, 先導的学際研究機構, 教授 (00379140)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000); Fiscal Year 2019: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2018: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
• Keywords: 酸化反応 / 酸素酸化 / 金属錯体 / 求電子剤 / ラジカル / 電子移動 / キノン / 分子状酸素 / フォトレドックス触媒 / 光反応 / フルオラス溶媒 / アルカン / Ｃ－Ｈ結合活性化 / 触媒

Outline of Annual Research Achievements

①基質カチオン（スーパー求電子剤）生成を経由した置換反応の開発
p-ベンゾキノン誘導体の光励起状態は強力な酸化力を用いて、炭化水素基質を電子移動酸化することが出来る。そこで生成した基質ラジカルカチオン種と水のような弱い求核剤との反応が十分期待できる。本研究では、ベンゼンラジカルカチオンをスーパー求電子剤として用いた場合、臭化水素水（HBr）を臭素源とする臭素フリーベンゼンの臭素化反応、アルコール（ROH)を使用したアルコキシル化、カルボチオレーション、アミノ化などが一段階で達成できる反応系を見いだした。この反応では、基質を酸化する際にアルコールなどの求核種を酸化しないように、適切な光触媒を選択する必要があったが、p-ベンゾキノン誘導体は、還元電位が0.2 V程度刻みに種々の置換p-ベンゾキノンが利用可能で、反応系に合わせた光触媒を選択することができた。
②酸化触媒を電子移動酸化して活性化することによるハイブリッド酸素化光触媒系の開発
アルケン類の酸素付加によるエポキシ化などの研究において高原子価金属オキソ錯体が有用であることは広く知られている。例えば、鉄（IV)オキソ錯体はシクロヘキセンをはじめとするアルケン類を容易に酸素化できるが、シクロヘキサンなどのアルカンは不可能であった。しかも高原子価金属オキソ錯体を調製するには、それ以上の酸化力を有する過酸化物などを使用する必要があった。本研究では、前述の2,3-ジクロロ-5,6-ジシアノ-p-ベンゾキノン（DDQ）の高い酸化力を利用することによって、高い酸化力を有する、鉄（IV)オキソ錯体をさらに電子移動酸化し、Fe(V)オキソ種を系中で発生させることができた。これにより高難度な炭化水素のＣ－Ｈ活性化が可能となった。

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

• [Int'l Joint Research] Roswell Park Cancer Center Institute/The University of Houston/University at Buffalo(米国)
• [Int'l Joint Research] Indian Institute of Chemical Technology(インド)
• [Int'l Joint Research] Theoretical and Physical Chemistry Inst.(ギリシャ)
• [Int'l Joint Research] Universidad Miguel Hernandez(スペイン)
• [Int'l Joint Research] 梨花女子大学(韓国)
• [Int'l Joint Research]
• [Int'l Joint Research] Ewha Womans University(韓国)
• [Int'l Joint Research] Kafrelsheikh University(エジプト)
• [Int'l Joint Research] Roswell Cancer Institute(米国)
• [Journal Article] Low switching voltage, high-stability organic phototransistor memory based on a photoactive dielectric and an electron trapping layer (2020)
  • Author(s): Dao Toan Thanh、Sakai Heisuke、Ohkubo Kei、Fukuzumi Shunichi、Murata Hideyuki
  • Journal Title: Organic Electronics Volume: 77 Pages: 105505-105505
  • DOI: 10.1016/j.orgel.2019.105505
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Paddlewheel Complexes with Azulenes: Electronic Interaction between Metal Centers and Equatorial?Ligands (2019)
  • Author(s): Tsuchiya Takahiro、Umemura Reiya、Kaminaga Mutsumi、Kushida Shunsuke、Ohkubo Kei、Noro Shin‐Ichiro、Mazaki Yasuhiro
  • Journal Title: ChemPlusChem Volume: 84 Issue: 6 Pages: 655-664
  • DOI: 10.1002/cplu.201800513
  • Peer Reviewed
• [Journal Article] Catalytic asymmetric allylation of aldehydes with alkenes through allylic C(sp3)-H functionalization mediated by organophotoredox and chiral chromium hybrid catalysis (2019)
  • Author(s): Mitsunuma Harunobu、Tanabe Shun、Fuse Hiromu、Ohkubo Kei、Kanai Motomu
  • Journal Title: Chemical Science Volume: 10 Issue: 12 Pages: 3459-3465
  • DOI: 10.1039/c8sc05677c
  • Peer Reviewed / Open Access
• [Journal Article] Photochemical C-H oxygenation of side-chain methyl groups in polypropylene with chlorine dioxide (2019)
  • Author(s): Ohkubo Kei、Asahara Haruyasu、Inoue Tsuyoshi
  • Journal Title: Chemical Communications Volume: 55 Issue: 32 Pages: 4723-4726
  • DOI: 10.1039/c9cc01037h
  • Peer Reviewed
• [Journal Article] Synthesis and radical-scavenging activity of C-methylated fisetin analogues (2019)
  • Author(s): 1.K. Imai, I. Nakanishi, K. Ohkubo, A. Ohno, M. Mizuno, S. Fukuzumi, K. Matsumoto, K. Fukuhara
  • Journal Title: Bioorg. Med. Chem. Volume: 27 Issue: 8 Pages: 1720-1727
  • DOI: 10.1016/j.bmc.2019.02.033
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A Diprotonated Porphyrin as an Electron Mediator in Photoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies (2019)
  • Author(s): W. Suzuki, H. Kotani, T. Ishizuka, M. Kawano, H. Sakai, T. Hasobe, K. Ohkubo, S. Fukuzumi, T. Kojima
  • Journal Title: The Journal of the Physical Chemistry C Volume: 123 Issue: 18 Pages: 11529-11538
  • DOI: 10.1021/acs.jpcc.9b02449
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] A Pyropheophorbide Analogue Containing a Fused Methoxy Cyclohexenone Ring System Shows Promising Cancer‐Imaging Ability (2019)
  • Author(s): Marko Aimee J.、Dukh Mykhaylo、Patel Nayan J.、Missert Joseph R.、Ohulchanskyy Tymish、Tabaczynski Walter A.、Ohkubo Kei、Fukuzumi Shunichi、Yao Rutao、Sajjad Munawwar、Pandey Ravindra K.
  • Journal Title: ChemMedChem Volume: 14 Issue: 16 Pages: 1503-1513
  • DOI: 10.1002/cmdc.201900352
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Kinetic Isotope Effect in the Reaction of Water-Soluble Antioxidants with Water-Solubilized 2,2-Diphenyl-1-picrylhydrazyl Radical in Aqueous Buffer Solutions (2019)
  • Author(s): 中西 郁夫，荘司 好美，大久保 敬，小澤 俊彦，松本 謙一郎
  • Journal Title: Free Radical Biology and Medicine Volume: 145 Pages: 34-34
  • DOI: 10.1016/j.freeradbiomed.2019.10.086
  • Peer Reviewed
• [Journal Article] Unified Mechanism of Oxygen Atom Transfer and Hydrogen Atom Transfer Reactions with a Triflic Acid-Bound Nonheme Manganese(IV) Oxo Complex via Outer-Sphere Electron Transfer (2019)
  • Author(s): Lee Yong-Min、Kim Surin、Ohkubo Kei、Kim Kyung-Ha、Nam Wonwoo、Fukuzumi Shunichi
  • Journal Title: Journal of the American Chemical Society Volume: 141 Issue: 6 Pages: 2614-2622
  • DOI: 10.1021/jacs.8b12935
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Assemblies of Boron Dipyrromethene/Porphyrin, Phthalocyanine, and C60 Moieties as Artificial Models of Photosynthesis: Synthesis, Supramolecular Interactions, and Photophysical Studies (2018)
  • Author(s): Chen, Xiao-Fei; El-Khouly, Mohamed E.; Ohkubo, Kei; Fukuzumi, Shunichi; Ng, Dennis K. P.
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 15 Pages: 3862-3872
  • DOI: 10.1002/chem.201705843
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A supramolecular photocatalyst composed of a polyoxometalate and a photosensitizing water-soluble porphyrin diacid for the oxidation of organic substrates in water (2018)
  • Author(s): Ishizuka, Tomoya; Ohkawa, Shumpei; Ochiai, Hidemi; Hashimoto, Muneaki; Ohkubo, Kei; Kotani, Hiroaki; Sadakane, Masahiro; Fukuzumi, Shunichi; Kojima, Takahiko
  • Journal Title: Green Chemistry Volume: 20 Issue: 9 Pages: 1975-1980
  • DOI: 10.1039/c8gc00295a
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Mechanistic Insights into Homogeneous Electrocatalytic and Photocatalytic Hydrogen Evolution Catalyzed by High-Spin Ni(II) Complexes with S2N2-Type Tetradentate Ligands (2018)
  • Author(s): Hong Dachao、Tsukakoshi Yuto、Kotani Hiroaki、Ishizuka Tomoya、Ohkubo Kei、Shiota Yoshihito、Yoshizawa Kazunari、Fukuzumi Shunichi、Kojima Takahiko
  • Journal Title: Inorganic Chemistry Volume: 57 Issue: 12 Pages: 7180-7190
  • DOI: 10.1021/acs.inorgchem.8b00881
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Long-Lived Photoexcited State of a Mn(IV)-Oxo Complex Binding Scandium Ions That is Capable of Hydroxylating Benzene (2018)
  • Author(s): Sharma Namita、Jung Jieun、Ohkubo Kei、Lee Yong-Min、El-Khouly Mohamed E.、Nam Wonwoo、Fukuzumi Shunichi
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 27 Pages: 8405-8409
  • DOI: 10.1021/jacs.8b04904
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Reaction of Glutathione and Bio-Related Thiols with 2,2-Diphenyl-1-picrylhydrazyl Radical Solubilized by β-Cyclodextrin in Water (2018)
  • Author(s): 中西 郁夫，大久保 敬，上野 恵美，関根(鈴木) 絵美子，小澤 俊彦，松本 謙一郎
  • Journal Title: Free Radical Biology and Medicine Volume: 120 Pages: S94-S94
  • DOI: 10.1016/j.freeradbiomed.2018.04.311
  • Peer Reviewed
• [Presentation] Photoredox Catalysts for Direct Phenol Production from Benzene (2020)
  • Author(s): Kei Ohkubo
  • Organizer: 4th International Conference on Catalysis and Chemical Engineering
  • Int'l Joint Research / Invited
• [Presentation] 除菌消臭剤の開発から生まれた化学反応～資源大国ニッポンへの道。それは興部から～ (2020)
  • Author(s): 大久保敬
  • Organizer: 興部高校セミナー
  • Invited
• [Presentation] 二酸化塩素を用いたメタンからメタノールへの光化学変換 (2020)
  • Author(s): 大久保敬
  • Organizer: マテリアルサイエンス系セミナー
  • Invited
• [Presentation] Supramolecular electron-transfer chemistry of lithium ion encapsulated fullerene with porphyrinoids (2019)
  • Author(s): Kei Ohkubo
  • Organizer: 4th Baltic Conference Series (4BCS)
  • Int'l Joint Research / Invited
• [Presentation] Photochemical C-H Oxygenation of Side-chain Methyl Groups in Polypropylene with Chlorine Dioxide (2019)
  • Author(s): Kei Ohkubo
  • Organizer: International Conference on Photocatalysis and Photoenergy-2019 (ICoPP2019)
  • Int'l Joint Research / Invited
• [Presentation] Selective Aerobic Oxygenation of Hydrocarbons Using Photoredox Catalysts (2019)
  • Author(s): Kei Ohkubo
  • Organizer: 3rd World Chemistry Conference and Exhibition (WCCE-2019)
  • Int'l Joint Research / Invited
• [Presentation] Light-Driven C-H Oxygenation of Methane into Methanol and Formic Acid by Chlorine Dioxide (2019)
  • Author(s): Kei Ohkubo
  • Organizer: The 29th International Conference on Photochemistry (ICP2019)
  • Int'l Joint Research / Invited
• [Presentation] 分子光触媒を用いた環境調和型有機合成反応 (2019)
  • Author(s): 大久保敬
  • Organizer: 大塚グループ有機合成セミナー
  • Invited
• [Presentation] 分子光触媒を用いた高選択的酸化反応 (2019)
  • Author(s): 大久保敬
  • Organizer: 岐阜薬科大学セミナー
  • Invited
• [Presentation] 有機フォトレドックス触媒を用いた選択的酸素化反応 (2019)
  • Author(s): 大久保敬
  • Organizer: 第54回有機反応若手の会
  • Invited
• [Presentation] 除菌消臭剤の有効成分を利用した化学反応 (2019)
  • Author(s): 大久保敬
  • Organizer: 第１回ファーマラボEXPO
  • Invited
• [Presentation] 二酸化塩素を用いたメタンの光酸化反応～反応活性種は除菌消臭剤の有効成分～ (2019)
  • Author(s): 大久保敬
  • Organizer: 先端シーズフォーラム
  • Invited
• [Presentation] 二酸化塩素を用いた光酸化反応～低分子メタンガスから高分子材料まで有機物なら何でも酸素官能基が導入できる新反応 (2019)
  • Author(s): 大久保敬
  • Organizer: イノベーションジャパン2019
  • Invited
• [Presentation] 有機フォトレドックス触媒を用いた選択的酸素化反応 (2019)
  • Author(s): 大久保敬
  • Organizer: 2019年有機反応機構研究会
  • Invited
• [Presentation] Metal-free Organic Transformation Using Organic Photoredox Catalysts (2019)
  • Author(s): 大久保敬
  • Organizer: 2019年光化学討論会
  • Invited
• [Presentation] 二酸化塩素を用いたメタンの光酸化反応～反応活性種は除菌消臭剤の有効成分～ (2019)
  • Author(s): 大久保敬
  • Organizer: 新潟大学セミナー
  • Invited
• [Presentation] Light-driven methane oxygenation with chlorine dioxide (2019)
  • Author(s): 大久保敬
  • Organizer: 錯体化学会第69回討論会
  • Invited
• [Presentation] 除菌消臭剤の有効成分を利用した化学反応 (2019)
  • Author(s): 大久保敬
  • Organizer: 大阪大学消化器外科セミナー
  • Invited
• [Presentation] 二酸化塩素を用いた光酸化反応～反応活性種は除菌消臭剤の有効成分～ (2019)
  • Author(s): 大久保敬
  • Organizer: 第３回電子移動アップデートフォーラム
  • Invited
• [Presentation] 二酸化塩素の光活性化によるプラスチック表面の機能化 (2019)
  • Author(s): 大久保敬
  • Organizer: 2019年度 第3回研究講演会
  • Invited
• [Presentation] Photooxygenation of Hydrocarbons with Molecular Oxygen by Electron Transfer (2018)
  • Author(s): Kei Ohkubo
  • Organizer: 233rd, ECS Meeting
  • Int'l Joint Research / Invited
• [Presentation] Photodriven C-H Oxygenation of Methane by Molecular Oxygen with Chlorine Dioxide (2018)
  • Author(s): Kei Ohkubo
  • Organizer: Second Japanese-Spanish Symposium in Organic Synthesis
  • Int'l Joint Research / Invited
• [Presentation] Photochemical Oxygenation of Methane into Methanol and Formic Acid with Chlorine Dioxide (2018)
  • Author(s): Kei Ohkubo
  • Organizer: 27th PhotoIUPAC Dublin 2018, International Symposium on Photochemistry
  • Int'l Joint Research
• [Presentation] Light-Driven Aerobic Oxygenation of Methane into Methanol and Formic Acid by Chlorine Dioxide (2018)
  • Author(s): Kei Ohkubo
  • Organizer: 43rd International Conference on Coordination Chemistry (ICCC2018)
  • Int'l Joint Research / Invited
• [Presentation] Photochemical Conversion of Methane into Methanol by Chlorine Dioxide in a Fluorous Solvent (2018)
  • Author(s): Kei Ohkubo
  • Organizer: European Advanced Materials Congress - 2018 (EAMC2018)
  • Int'l Joint Research / Invited
• [Presentation] Supramolecular Electrochemical Cell of Lithium Ion Encapsulated Fullerene with Porphyrinoids (2018)
  • Author(s): Kei Ohkubo
  • Organizer: The 2nd Int'l Conference on Electrochemistry and Energy Storage (CEES 2018)
  • Int'l Joint Research / Invited
• [Presentation] Methane/Methanol Conversion by Photochemical Activation of Chlorine Dioxide Radical (2018)
  • Author(s): Kei Ohkubo
  • Organizer: 3rd International Conference and Expo on Petrochemistry & Natural Resources
  • Int'l Joint Research / Invited
• [Presentation] Light-driven Oxygenation of Methane to Methanol and Formic Acid with Chlorine Dioxide (2018)
  • Author(s): Kei Ohkubo
  • Organizer: 14th Korea-Japan Frontier Photoscience 2018 (KJFP-2018)
  • Int'l Joint Research / Invited
• [Presentation] Photochemical Oxygenation of Methane into Methanol with Molecular Oxygen and Chlorine Dioxide Radical (2018)
  • Author(s): Kei Ohkubo
  • Organizer: 13th International Symposium on Organic Reactions (ISOR-13)
  • Int'l Joint Research / Invited
• [Presentation] Aerobic Methane Oxygenation to Methanol with Chlorine Dioxide Radical (2018)
  • Author(s): Kei Ohkubo
  • Organizer: 3rd International Conference on Catalysis and Chemical Engineering
  • Int'l Joint Research / Invited
• [Presentation] Aerobic Methane Oxygenation to Methanol with Chlorine Dioxide Radical (2018)
  • Author(s): Kei Ohkubo
  • Organizer: 2nd International Conference on Chemistry
  • Int'l Joint Research / Invited
• [Presentation] 水溶性ポルフィリノイドの光増感一重項酸素生成の近赤外発光検出 (2018)
  • Author(s): 大久保敬, 大澤祥宏
  • Organizer: 第８回ポルフィリン‐ALA学会年会
• [Presentation] 炭化水素の酸素酸化を可能にするハイブリッド光触媒系の開発 (2018)
  • Author(s): 大久保敬
  • Organizer: 第2回 ハイブリッド触媒リトリート
• [Presentation] 二酸化塩素を用いた高分子表面光酸化反応 (2018)
  • Author(s): 浅原時泰, 井上豪, 大久保 敬
  • Organizer: 第7回JACI/GSC シンポジウム
• [Presentation] 二酸化塩素によるメタンからメタノールとギ酸への光酸化反応 (2018)
  • Author(s): 大久保敬
  • Organizer: 第7回JACI/GSC シンポジウム
• [Presentation] 二酸化塩素光酸化によって作成した酸化ポリプロピレン表面とアルミニウムの接着 (2018)
  • Author(s): 賈燕坤, 浅原時泰, 麻生隆彬, 井上豪, 大久保敬, 宇山浩
  • Organizer: 第7回JACI/GSC シンポジウム
• [Presentation] 二酸化塩素によるポリN-イソプロピルアクリルアミドの表面酸化反応 (2018)
  • Author(s): 三浦良将, 浅原時泰, 麻生隆彬, 宇山浩, 大久保敬, 井上豪
  • Organizer: 第7回JACI/GSC シンポジウム
• [Presentation] 二酸化塩素によるメタンの光酸素酸化反応 (2018)
  • Author(s): 大久保 敬、浅原時泰, 井上豪
  • Organizer: 2018年光化学討論会
• [Presentation] 二酸化塩素を用いたポリオレフィン表面の光酸化 (2018)
  • Author(s): 浅原時泰, 井上豪, 大久保 敬
  • Organizer: 第29回基礎有機化学討論会
• [Presentation] フルオラス溶媒を用いたメタン・メタノール変換反応 (2018)
  • Author(s): 大久保敬
  • Organizer: フルオラス研究会第11回シンポジウム
  • Invited
• [Presentation] 二酸化塩素を用いたアルカンおよび高分子表面の選択的光酸素化反応 (2018)
  • Author(s): 大久保 敬, 浅原時泰, 井上豪
  • Organizer: 二酸化塩素を用いたアルカンおよび高分子表面の選択的光酸素化反応
• [Presentation] 光酸化法を用いた新規メッキ前処理技術 (2018)
  • Author(s): 浅原時泰,賈燕坤, 麻生隆彬, 大久保 敬, 宇山浩, 井上豪
  • Organizer: 第99日本化学会春季年会
• [Presentation] 2-アザフルオレノンを機能性リガンドとした新規光触媒合成 (2018)
  • Author(s): 浅原時泰, 堀川由利江, 大久保敬, 西脇永敏
  • Organizer: 第99日本化学会春季年会
• [Presentation] 二酸化塩素を用いたプラスチック表面の選択的光酸素化反応 (2018)
  • Author(s): 大久保 敬, 浅原時泰, 井上豪
  • Organizer: 第99日本化学会春季年会
• [Remarks] 大久保研ＨＰ
  • URL: http://www.irdd.osaka-u.ac.jp/ohkubo/Ohkubo_Lab/Top.html