Creation of Bioinspired Catalysts with Specific Fields

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 16H01035
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyushu University
• Principal Investigator: 久枝 良雄 九州大学, 工学研究院, 教授 (70150498)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2017: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2016: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: ビタミンB12 / 光反応 / 脱ハロゲン化反応 / トリフルオロメチル化反応 / パーフルオロアルキル化反応 / バイオインスパイアード / 電解反応 / ナノ空間材料 / バイオインスパイアード触媒 / 金属錯体 / 光増感剤 / 酸化還元反応 / 電気化学反応 / 酸化チタン / 反応場 / 還元反応 / 酸化反応 / 生体関連金属錯体 / デュエット反応

Outline of Annual Research Achievements

金属酵素は天然のナノハイブリッド触媒であり、反応は高活性・高選択的に進行し理想的な触媒系の１つである。しかし、構造安定性に欠け、そのまま用いるには応用範囲が狭いなどの欠点も多い。本研究では、酵素の精緻な反応場特性のエッセンスを抽出し、それを反映したナノ空間材料とモデル錯体の組み合わせによりバイオインスパイアード触媒を構築する。すなわち酵素反応場を意識した触媒系を構築し、天然酵素を凌駕する革新的触媒の開発を目指している。昨年度は、酸化チタンとビタミンB12誘導体のハイブリッド触媒の開発と空気下での新規な反応系の開発に成功した。今年度は、電気化学的活性化法を用い、ビタミンB12誘導体を用いたトリフルオロメチル化反応およびパーフルオロアルキル化反応の開発に成功した。
ビタミンB12誘導体の活性種であるCo(I)種とCF3Iの反応によりCo-CF3結合を有する錯体を合成した。得られたCF3錯体は可視光照射下でホモリシス開裂し、CF3ラジカルを生成することを見出した。そこで天然由来のビタミンB12誘導体を用いて、オレフィン等の有機化合物のCF3化反応を行った。
１mol%のビタミンB12誘導体を触媒として用い、メタノールを媒体とし、種々のアレーン類のトリフルオロメチル化反応およびパーフルオロアルキル化反応を行った。電解セルとしては１液型のものを使用し、動作極に白金網、対極に亜鉛を用い定電位電解反応を行った。基質には種々のアレーン類を添加し、ヨウ化トリフルオロメチルまたはヨウ化パーフルオロアルキルをシリンジポンプで注入して触媒反応を行った。電子豊富なアレーン類のトリフルオロメチル化およびパーフルオロアルキル化反応が効率良く進行した。また、選択的に1カ所のみのトリフルオロメチル化およびパーフルオロアルキル化が進行した。

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Polish Academy of Science(Poland)
• [Journal Article] Hybrid Catalyst for Light-Driven Green Molecular Transformations (2017)
  • Author(s): H. Shimakoshi, Y. Hisaeda
  • Journal Title: ChemPlusChem Volume: 82 Issue: 1 Pages: 18-29
  • DOI: 10.1002/cplu.201600303
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Facile synthesis of 9,10,19,20-tetraalkylporphycenes (2017)
  • Author(s): T. Ono, D. Koga, Y. Hisaeda
  • Journal Title: Chem. Lett. Volume: 46 Issue: 2 Pages: 260-262
  • DOI: 10.1246/cl.161019
  • NAID: 130005317145
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Cathodic Reductive Couplings and Hydrogenations of Alkenes and Alkynes Catalyzed by the B12 Model Complex (2017)
  • Author(s): H. Shimakoshi, Z. Luo, K. Tomita, Y. Hisaeda
  • Journal Title: J. Organomet. Chem. Volume: 印刷中 Pages: 71-77
  • DOI: 10.1016/j.jorganchem.2017.02.002
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Significant enhancement of visible light photocatalytic activity of the hybrid B12-PIL/rGO in the presence of Ru(bpy)32+ for DDT dehalogenation (2017)
  • Author(s): Ying Sun, Wei Zhang, Jian Tong, Yu Zhang, Shuyao Wu, Daliang Liu, Hisashi Shimakoshi, Yoshio Hisaeda, Xi-Ming Song
  • Journal Title: RSC Advances Volume: 7 Issue: 31 Pages: 19197-19204
  • DOI: 10.1039/c7ra02062g
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Inclusion crystal growth and optical properties of organic charge transfer complexes built from small aromatic guest molecules and naphthalenediimide derivatives (2017)
  • Author(s): T. Ono, Y. Tsukiyama, A. Taema, Y. Hisaeda
  • Journal Title: Chem. Lett. Volume: 印刷中 Issue: 6 Pages: 801-804
  • DOI: 10.1246/cl.170122
  • NAID: 130005689370
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Photocatalytic alkene reduction by a B12-TiO2 hybrid catalyst coupled with C-F bond cleavage for gem-difluoroolefin synthesis (2017)
  • Author(s): Tian Hui、Shimakoshi Hisashi、Imamura Kenji、Shiota Yoshihito、Yoshizawa Kazunari、Hisaeda Yoshio
  • Journal Title: Chem. Commun. Volume: 53 Issue: 68 Pages: 9478-9481
  • DOI: 10.1039/c7cc04377e
  • Peer Reviewed
• [Journal Article] Impact of the corrin framework of vitamin B12 on the electrochemical carbon-skeleton rearrangement in comparison to an imine/oxime planar ligand; tuning selectivity in 1,2-migration of a functional group by controlling electrolysis potential (2017)
  • Author(s): K. Tahara, L. Pan, R. Yamaguchi, H. Shimakoshi, M. Abe, Y. Hisaeda
  • Journal Title: J. Inorg. Biochem. Volume: 175 Pages: 239-243
  • DOI: 10.1016/j.jinorgbio.2017.07.021
  • Peer Reviewed
• [Journal Article] A Vitamin B12 Derivative Catalyzed Electrochemical Trifluoromethylation and Perfluoroalkylation of Arenes and Heteroarenes in Organic Media (2017)
  • Author(s): M. J. Hossain, T. Ono, K. Wakiya, Y. Hisaeda
  • Journal Title: Chem. Commun. Volume: 53 Issue: 79 Pages: 10878-10881
  • DOI: 10.1039/c7cc06221d
  • Peer Reviewed
• [Journal Article] meso-Tetraaryl(porphyrinato)cobalt(III)-Catalyzed Oxygenation of Disilanes under Aerobic Conditions (2017)
  • Author(s): J. Ohshita, Y. Matsumura, T. Nakayama, H. Yoshida, A. Kunai, Y. Hisaeda, T. Hayashi
  • Journal Title: Chem. Lett. Volume: 46 Issue: 12 Pages: 1807-1809
  • DOI: 10.1246/cl.170857
  • NAID: 130006243159
  • Peer Reviewed
• [Journal Article] The first synthesis of mesodicycloalkylporphycenes: ring strain effects on structural and optical properties of isomeric porphyrins (2017)
  • Author(s): T. Ono, D. Koga, K. Yoza, Y. Hisaeda
  • Journal Title: Chem. Commun. Volume: 53 Issue: 91 Pages: 12258-12261
  • DOI: 10.1039/c7cc07170a
  • Peer Reviewed
• [Journal Article] Supramolecular System Composed of B12 Model Complex and Organic Photosensitizer: Impact of the Corrin Framework of B12 on the Visible-Light-Driven Dechlorination without the Use of Noble Metals (2016)
  • Author(s): K. Tahara, K. Mikuriya, T. Masuko, J. Kikuchi, Y. Hisaeda
  • Journal Title: Supramolecular Chemistry Volume: 28 Issue: 1-2 Pages: 141-150
  • DOI: 10.1080/10610278.2015.1103373
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Intraprotein transmethylation via a CH3–Co(III) species in myoglobin reconstituted with a cobalt corrinoid complex (2016)
  • Author(s): Y. Morita, K. Oohora, A. Sawada, K. Doitomi, J. Ohbayashi, T. Kamachi, K. Yoshizawa, Y. Hisaeda, T. Hayashi
  • Journal Title: Dalton Transactions Volume: 45 Issue: 8 Pages: 3277-3284
  • DOI: 10.1039/c5dt04109k
  • Peer Reviewed / Open Access
• [Journal Article] Electrochemistry and Catalytic Properties of Amphiphilic Vitamin B12 Derivatives in Nonaqueous Media (2016)
  • Author(s): M. Giedyk, H. Shimakoshi, K. Goliszewska, D. Gryko, Y. Hisaeda
  • Journal Title: Dalton Trans Volume: 45 Issue: 20 Pages: 8340-8346
  • DOI: 10.1039/c6dt00355a
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Electrolysis of Trichloromethylated Organic Compounds under Aerobic Conditions Catalyzed by B12 Model Complex for Ester and Amide Formations (2016)
  • Author(s): H. Shimakoshi, Z. Luo, T. Inaba, Y. Hisaeda
  • Journal Title: Dalton Trans. Volume: 45 Issue: 25 Pages: 10173-10180
  • DOI: 10.1039/c6dt00556j
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Bioinspired Catalysts with Vitamin B12 Function Activated by Photochemical and Electrochemical Methods (2017)
  • Author(s): Yoshio Hisaeda
  • Organizer: 2nd International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research / Invited
• [Presentation] Bioinspired Catalyst with Vitamin B12 Functions Activated by Photochemical or Electrochemical Methods (2017)
  • Author(s): Yoshio Hisaeda
  • Organizer: 26th International Conference on Coordination and Bioinorganic Chemistry
  • Int'l Joint Research / Invited
• [Presentation] 生体関連色素の化学 “ビタミンB12酵素から学ぶバイオインスパイアード触媒” (2017)
  • Author(s): 久枝良雄
  • Organizer: ブルカー・バイオスピン株式会社 九州サービスセンター開所記念セミナー
  • Invited
• [Presentation] Bioinspired Catalytic Reactions Using Vitamin B12 Derivative (2017)
  • Author(s): Yoshio Hisaeda
  • Organizer: 6th Asian Conference on Coordination Chemistry(
  • Int'l Joint Research / Invited
• [Presentation] 光化学的手法を用いたバイオインスパイアード触媒の開発 (2017)
  • Author(s): 久枝良雄
  • Organizer: 第29回配位化合物の光化学討論会
  • Invited
• [Presentation] 人工酵素 バイオインスパイアード触媒 (2017)
  • Author(s): 久枝良雄
  • Organizer: 化学物質評価研究機構(CERI) 寄付講座 CERI公開講座 「先端材料化学から設計、構造・物性から機能化まで」
  • Invited
• [Presentation] Bioinspired Catalyst with Vitamin B12 Functions Using Photochemical and Electrochemical Methods (2017)
  • Author(s): Yoshio Hisaeda
  • Organizer: 5th CMS International Symposium (CMS-5) on Photofunctional Chemistry and Molecular Systems
  • Invited
• [Presentation] 光および電気化学活性化を用いたバイオインスパイアード触媒の創製 (2017)
  • Author(s): 久枝良雄
  • Organizer: 群馬大学元素科学国際教育研究センター主催講演会
  • Invited
• [Presentation] Bioinspired Catalytic Reaction Lessons from Vitamin B12 Enzyme (2016)
  • Author(s): Yoshio Hisaeda
  • Organizer: 8th Asian Biological Inorganic Chemistry Conference (AsBIC8-2016)
  • Place of Presentation: Auckland, New Zealand
  • Year and Date: 2016-12-06
  • Int'l Joint Research / Invited
• [Presentation] Bioinspired Catalysts with Vitamin B12 Derivatives Using Photochemical and Electrochemical Methods (2016)
  • Author(s): Yoshio Hisaeda
  • Organizer: International Symposium on Catalysis and Fine Chemicals in Taipei-2016 (C&FC-2016)
  • Place of Presentation: Taipei, Taiwan
  • Year and Date: 2016-11-12
  • Int'l Joint Research / Invited
• [Presentation] Bioinspired Catalysts based on Vitamin B12 Chemistry (2016)
  • Author(s): Yoshio Hisaeda
  • Organizer: 9th International Conference on Porphyrins & Phthalocyanines(ICPP-9)
  • Place of Presentation: Nanjing, China
  • Year and Date: 2016-07-05
  • Int'l Joint Research / Invited
• [Presentation] Bioinspired Catalysts with Vitamin B12 Functions Using Photosensitizer or Electrochemical Method (2016)
  • Author(s): Yoshio Hisaeda
  • Organizer: The 12th International Symposium on Organic Reactions and The 6th German-Japanese Symposium on Electrosynthesis (ISOR-12 and GJSE-6)
  • Place of Presentation: 京都
  • Year and Date: 2016-04-22
  • Int'l Joint Research / Invited
• [Presentation] ARTIFICIAL ENZYMES COMPOSED OF PHOTOSENSITIZER AND VITAMIN B12 DERIVATIVE (2016)
  • Author(s): Yoshio Hisaeda, Hisashi Shimakoshi, Takahiro Masuko, and Toshikazu Ono
  • Organizer: 26th IUPAC Symposium on Photochemistry
  • Place of Presentation: 大阪
  • Year and Date: 2016-04-06
  • Int'l Joint Research / Invited