ビタミンB12酵素に学ぶ感応性化学種の制御と触媒機能

• Project Area: Stimuli-responsive Chemical Species for the Creation of Functional Molecules
• Project/Area Number: 15H00952
• 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): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000); Fiscal Year 2016: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000); Fiscal Year 2015: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: ビタミンB12 / 電解反応 / 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 / 酸化還元反応 / ラジカル種 / 触媒反応 / 有機金属錯体 / 生体関連金属錯体 / 電気化学反応 / 光増感剤 / コバルト-炭素結合 / 光反応

Outline of Annual Research Achievements

B12依存性酵素は、ビタミンB12（化学名：コバラミン）を補酵素として10種類以上の多彩な代謝反応の触媒として働いている。その活性種はCo-C結合をもつコバルトアルキル錯体であり、光や熱により活性種を生成する感応性化学種である。このCo-C結合は、次の３種類の方法により合成できる。１）超求核性のCo(I)種とハロゲン化アルキルのような親電子剤との反応、２）ラジカル特性を持つCo(II)種と有機ラジカルとの反応、３）Co(III)種とグリニヤール試薬のような求核剤との反応、によりCo-C結合は生成できる。このCo-C結合をもつコバルトアルキル錯体は、光・熱・酸化還元という外部刺激により開裂し、ラジカルやアニオン種のような短寿命活性種を生成する。本研究ではB12酵素の反応機構に学び、温和な条件でCo(I)種を生成できる反応系を見出し、感応性化学種であるコバルトアルキル錯体を経由した画期的な物質変換反応を開拓する。本研究では、モデル系での触媒反応の成功例の少ないメチル基転移反応に焦点を当て、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新触媒としての応用を検討した。
1,3,5-trimethoxybenzene(5.0×10-2 M)を基質として触媒量の1(5.0×10-4 M)を-0.8 V vs. Ag/AgClで電解・光照射しながらCF3Iを30分毎に基質に対して約2当量添加した。直ちに基質のCF3化が進行し、5時間後には収率が56%（触媒回転率56）であった。溶媒、反応電位、試薬の添加法を検討し、ベストな条件を見出した。次に、C3F7I, C4F9I, C5F11I, C6F13I, C7F15I, C8F17Iについて反応を行い、いずれも80％の高収率で反応が進行することを見出した。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [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] 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] 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
• [Journal Article] Oxygen-Controlled Catalysis of B12-TiO2: Formation of Ester and Amide from Trichlorinated Organic Compounds by Photoirradiation (2015)
  • Author(s): Hisashi Shimakoshi, Yoshio Hisaeda
  • Journal Title: Angewandte Chemie International Edition Volume: 54 Issue: 51 Pages: 15439-15443
  • DOI: 10.1002/anie.201507782
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Crystal Structure Dependence for Reactivities of B12-TiO2 Hybrid Catalysts with Anatase and Rutile Forms (2015)
  • Author(s): Shiamkoshi, H.; Nagami, Y.; Hisaeda, Y.
  • Journal Title: Rapid Communication in Photoscience Volume: 未定 Issue: 1 Pages: 9-11
  • DOI: 10.5857/rcp.2015.4.1.9
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Development of Metal-Organic Framework (MOF)-B12 system as new bio-inspired heterogeneous catalyst (2015)
  • Author(s): Xu, J.; Shimakoshi, H.; Hisaeda, Y.
  • Journal Title: J. Organometal. Chem. Volume: 782 Pages: 89-95
  • DOI: 10.1016/j.jorganchem.2014.11.015
  • Peer Reviewed / Acknowledgement Compliant
• [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
• [Presentation] Article Enzymes Composed of Vitamin B12 Derivative and Photosensitizers (2015)
  • Author(s): Yoshio Hisaeda
  • Organizer: The 7th Asia and Oceania Conference on Photobiology
  • Place of Presentation: 台湾・台北市・Academia Sinica
  • Year and Date: 2015-11-15
  • Int'l Joint Research / Invited
• [Presentation] Bioinspired Catalysts Composed of Vitamin B12 Derivative and Photosensitizers (2015)
  • Author(s): Yoshio HISAEDA
  • Organizer: 第2回日英ジョイントシンポジウム
  • Place of Presentation: 奈良県奈良市・奈良女子大学
  • Year and Date: 2015-09-20
  • Int'l Joint Research / Invited
• [Presentation] Photochemical and Electrochemical Trifluoromethylation Catalyzed by Vitamin B12 Derivative (2015)
  • Author(s): Yoshio Hisaeda, Kosuke Wakiya, Toshikazu Ono, and Hisashi Shimakoshi
  • Organizer: The 11th Korean-Japan Stmposium on Frontier Photoscience-2015
  • Place of Presentation: 大韓民国済州島・Bareve Hotel
  • Year and Date: 2015-06-26
  • Int'l Joint Research / Invited
• [Presentation] Bio-inspired Catalysts Learned from B12 Enzyme for Degradation of Environmental Pollutants (2015)
  • Author(s): Yoshio Hisaeda
  • Organizer: XXV. INTERNATIONAL CONFERENCE ON COORDINATION AND BIOINORGANIC CHEMISTRY (ICCBIC-25)
  • Place of Presentation: Smolenice, Slovakia
  • Year and Date: 2015-05-31
  • Int'l Joint Research / Invited