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: 18H04265
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• 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): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2019: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: ビタミンB12 / ラジカル反応 / コバルト-炭素結合 / パーフルオロアルキル化 / ジフルオロアルキル化 / 電気化学 / 触媒反応 / 有機金属錯体 / 生体関連金属錯体 / 電気化学的活性化 / バイオインスパイアード / 環状ピロール化合物 / 光増感剤 / 酸化還元反応 / フルオロアルキル化反応

Outline of Annual Research Achievements

ビタミンB12は生体内の様々な酵素反応に関与し、特にラジカル反応に対し高い耐性を持つ天然の有機金属錯体である。なかでも中心金属のコバルトと軸配位子のアルキル基とのコバルト-炭素結合(Co-C)の生成機構、およびそのホモリシス開裂により生じるアルキルラジカルの生成は、生物無機化学、有機金属化学、触媒化学の観点から興味深い。昨年度までに天然のビタミンB12を誘導体化したコバルト錯体を利用した有機化合物へのトリフルオロメチル化、パーフルオロアルキル化、ジフルオロアルキル化反応を報告した。今年度は、本系の拡張を目的として、ビタミンB12誘導体と同様の電気化学的挙動を示すことが知られるimine/oxime-typeコバルト錯体（C1）に着目し、これを触媒とした有機化合物へのフルオロアルキル化反応を検討した。具体的には、錯体（C1）を触媒として、電極表面を反応場とした触媒反応系の構築、およびインドールやアニリン誘導体に対するフルオロアルキル化反応を実施した。
１mol%の錯体 (C1)を触媒として用い、インドールとアニリン誘導体の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 -0.80 V vs. Ag/AgClの条件で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、フルオロアルキル源(n-C4F9I)をシリンジポンプで注入して触媒反応を行った。生成物はＮＭＲおよび単結晶Ｘ線構造解析により同定し、GC-MSおよびNMRにより収率を算出した。種々の条件を検討し、効率的なフルオロアルキル化反応を達成した。ラジカルトラップ実験により、コバルト錯体のラジカル発生能を介した触媒反応であることが示唆された。コバルト-炭素結合(Co-C)を利用したフルオロアルキル化反応は新しいタイプの触媒系であり、非常に興味深い。

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] Polish Academy of Science(ポーランド)
• [Int'l Joint Research] ポーランド科学アカデミー(ポーランド)
• [Journal Article] Mechanistic Study on Ring-Contracting Skeletal Rearrangement from Porphycene to Isocorrole by Experimental and Theoretical Methods (2020)
  • Author(s): Koide Taro、Maeda Takafumi、Abe Tsukasa、Shiota Yoshihito、Yano Yoshio、Ono Toshikazu、Yoshizawa Kazunari、Hisaeda Yoshio
  • Journal Title: European Journal of Organic Chemistry Volume: 2020 Issue: 12 Pages: 1811-1816
  • DOI: 10.1002/ejoc.201901659
  • Peer Reviewed / Open Access
• [Journal Article] Electrochemical properties and catalytic reactivity of cobalt complexes with redox-active meso-substituted porphycene ligands (2020)
  • Author(s): Koide Taro、Zhou Zihan、Xu Ning、Yano Yoshio、Ono Toshikazu、Luo Zhongli、Shimakoshi Hisashi、Hisaeda Yoshio
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 24 Issue: 01n03 Pages: 90-97
  • DOI: 10.1142/s1088424619500780
  • Peer Reviewed
• [Journal Article] Visible light-driven photocatalytic duet reaction catalyzed by the B12-rhodium-titanium oxide hybrid catalyst (2020)
  • Author(s): Shichijo Keita、Fujitsuka Mamoru、Hisaeda Yoshio、Shimakoshi Hisashi
  • Journal Title: Journal of Organometallic Chemistry Volume: 907 Pages: 121058-121058
  • DOI: 10.1016/j.jorganchem.2019.121058
  • Peer Reviewed
• [Journal Article] Aerobic oxidation of thioglycol catalysed by metallophthalocyanine in an organic-inorganic hybrid vesicle “cerasome” (2020)
  • Author(s): Zhang Guolin、Zhang Li、Zhang Dan、Wu Qiuhua、Sasaki Yoshihiro、Hisaeda Yoshio、Yasuhara Kazuma、Kikuchi Jun-ichi、Song Xi-Ming
  • Journal Title: Inorganic Chemistry Communications Volume: 115 Pages: 107866-107866
  • DOI: 10.1016/j.inoche.2020.107866
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Redox behaviour of the β-dihydroporphycene cobalt complex: study on the effect of hydrogenation of the ligand (2019)
  • Author(s): Hashimoto Koichi, Koide Taro, Okawara Toru, Shimakoshi Hisashi, Hori Yuta, Shiota Yoshihito, Yoshizawa Kazunari, Hisaeda Yoshio
  • Journal Title: Dalton Transactions Volume: 48 Issue: 3 Pages: 872-881
  • DOI: 10.1039/c8dt03743d
  • Peer Reviewed
• [Journal Article] Flexible-color tuning and white-light emission in three-, four-, and five-component host/guest co-crystals by charge-transfer emissions as well as effective energy transfers (2019)
  • Author(s): Toshikazu Ono, Yoshio Hisaeda
  • Journal Title: J. Mater. Chem. C Volume: 7 Issue: 10 Pages: 2829-2842
  • DOI: 10.1039/c8tc06165c
  • Peer Reviewed
• [Journal Article] Redox active ionic liquid as efficient mediator and solvent for visible light-driven B12 catalytic reactions (2019)
  • Author(s): Shimakoshi Hisashi、Houfuku Noriyuki、Chen Li、Hisaeda Yoshio
  • Journal Title: Green Energy & Environment Volume: 4 Issue: 2 Pages: 116-120
  • DOI: 10.1016/j.gee.2019.03.001
  • Peer Reviewed
• [Journal Article] Visible Light‐Driven, Room Temperature Heck‐Type Reaction of Alkyl Halides with Styrene Derivatives Catalyzed by B 12 Complex (2019)
  • Author(s): Chen Li、Hisaeda Yoshio、Shimakoshi Hisashi
  • Journal Title: Advanced Synthesis & Catalysis Volume: 361 Issue: 12 Pages: 2877-2884
  • DOI: 10.1002/adsc.201801707
  • Peer Reviewed
• [Journal Article] Highly malleable haem-binding site of the haemoprotein HasA permits stable accommodation of bulky tetraphenylporphycenes (2019)
  • Author(s): Sakakibara,E.; Shisaka,Y.; Iwai, Y.; Yamada, S.; Uehara, H.; Tosha, T.; Sugimoto, H.; Shiro, Y.; Stanfield, J. K.; Ogawa, K.; Watanabe, Y.; Shoji, O.
  • Journal Title: RSC Advances Volume: 9(32) Issue: 32 Pages: 18697-18702
  • DOI: 10.1039/c9ra02872b
  • Peer Reviewed / Open Access
• [Journal Article] Learning From Vitamin B12‐Mediated Reactions: Cobalt(III)－Carbon‐Assisted Catalytic C－H Difluoroacylation of (Hetero)Arenes through Controlled‐Potential Electrolysis (2019)
  • Author(s): Md. J. Hossain, Toshikazu Ono, Yoshio Yano, Yoshio Hisaeda
  • Journal Title: ChemElectroChem Volume: － Issue: 16 Pages: 4199-4203
  • DOI: 10.1002/celc.201900164
  • Peer Reviewed
• [Journal Article] Symmetry Reduction of Porphycenes with Finely Tuned Optical and Electronic Properties through Oxidative Cyclization of E / Z ‐Mixed Dipyrroethenes (2019)
  • Author(s): Xu Ning、Ono Toshikazu、Hisaeda Yoshio
  • Journal Title: Chemistry A European Journal Volume: 25 Issue: 50 Pages: 11680-11687
  • DOI: 10.1002/chem.201902080
  • Peer Reviewed
• [Journal Article] Salt-cocrystal continuum for photofunction modulation: stimuli-responsive fluorescence color-tuning of pyridine-modified intramolecular charge-transfer dyes and acid complexes (2019)
  • Author(s): Yano Yoshio、Ono Toshikazu、Hatanaka Sou、Gryko Daniel T.、Hisaeda Yoshio
  • Journal Title: Journal of Materials Chemistry C Volume: 7 Issue: 29 Pages: 8847-8854
  • DOI: 10.1039/c9tc02524c
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Inclusion crystals as vapochromic chemosensors: fabrication of a mini-sensor array for discrimination of small aromatic molecules based on side-chain engineering of naphthalenediimide derivatives (2019)
  • Author(s): Ono Toshikazu、Tsukiyama Yoshifumi、Hatanaka Sou、Sakatsume Yuma、Ogoshi Tomoki、Hisaeda Yoshio
  • Journal Title: Journal of Materials Chemistry C Volume: 7 Issue: 31 Pages: 9726-9734
  • DOI: 10.1039/c9tc03140e
  • Peer Reviewed
• [Journal Article] Synthesis of a meso-Tetraalkylporphycene Bearing Reactive Sites: Toward Porphycene-Polydimethylsiloxane Hybrids with Enhanced Photophysical Properties (2019)
  • Author(s): Ono Toshikazu、Shinjo Hyuga、Koga Daiki、Hisaeda Yoshio
  • Journal Title: European Journal of Organic Chemistry Volume: 2019 Issue: 46 Pages: 7578-7583
  • DOI: 10.1002/ejoc.201901497
  • Peer Reviewed
• [Journal Article] Visible light-driven cross-coupling reactions of alkyl halides with phenylacetylene derivatives for C(sp3)?C(sp) bond formation catalyzed by a B12 complex (2019)
  • Author(s): Chen Li、Kametani Yohei、Imamura Kenji、Abe Tsukasa、Shiota Yoshihito、Yoshizawa Kazunari、Hisaeda Yoshio、Shimakoshi Hisashi
  • Journal Title: Chemical Communications Volume: 55 Issue: 87 Pages: 13070-13073
  • DOI: 10.1039/c9cc06185a
  • Peer Reviewed
• [Journal Article] Tris(pentafluorophenyl)borane‐pyrrolo[3,2‐ b ]pyrrole Hybrids: Solid‐State Structure and Crystallization‐Induced Enhanced Emission (2019)
  • Author(s): Hatanaka Sou、Ono Toshikazu、Yano Yoshio、Gryko Daniel T.、Hisaeda Yoshio
  • Journal Title: ChemPhotoChem Volume: 4 Issue: 2 Pages: 138-143
  • DOI: 10.1002/cptc.201900192
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Visible Light‐Driven, One‐pot Amide Synthesis Catalyzed by the B 12 Model Complex under Aerobic Conditions (2018)
  • Author(s): Tian Hui、Shimakoshi Hisashi、Ono Toshikazu、Hisaeda Yoshio
  • Journal Title: ChemPlusChem Volume: 84 Issue: 3 Pages: 237-240
  • DOI: 10.1002/cplu.201800522
  • Peer Reviewed
• [Journal Article] Photocatalytic function of the B12 complex with the cyclometalated iridium(III) complex as a photosensitizer under visible light irradiation (2018)
  • Author(s): H. Tian, H, Shimakoshi, S. Kim, G. Park, Y. You, Y. Hisaeda
  • Journal Title: Dalton Transactions Volume: 47 Issue: 3 Pages: 675-683
  • DOI: 10.1039/c8dt90007h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Electrochemistry and catalytic properties of vitamin B12 derivatives in nonaqueous media (2018)
  • Author(s): H. Shimakoshi, Y. Hisaeda
  • Journal Title: Current Opinion in Electrochemistry Volume: 8 Pages: 24-30
  • DOI: 10.1016/j.coelec.2017.12.001
  • Peer Reviewed
• [Journal Article] First entry into nonmetal-centred porphycenes: synthesis of a phosphorus (V) complex of octaethylporphycene (2018)
  • Author(s): Abe Masaaki, Hiroto Mukotaka, Taro Fujioka, Toru Okawara, Kei Umegaki, Toshikazu Ono, Yoshio Hisaeda
  • Journal Title: Dalton Transactions Volume: 47 Issue: 8 Pages: 2487-2491
  • DOI: 10.1039/c7dt04471b
  • Peer Reviewed
• [Journal Article] Piezofluorochromism in Charge‐Transfer Inclusion Crystals: The Influence of High Pressure versus Mechanical Grinding (2018)
  • Author(s): Toshikazu Ono, Yoshifumi Tsukiyama, Ai Taema, Hiroyasu Sato, Hidetoshi Kiyooka, Yuma Yamaguchi, Ayumi Nagahashi, Manami Nishiyama, Yuichi Akahama, Yoshiki Ozawa, Masaaki Abe, Yoshio Hisaeda
  • Journal Title: ChemPhotoChem Volume: 印刷中 Issue: 5 Pages: 416-420
  • DOI: 10.1002/cptc.201700227
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of Trifluoromethylated B12 Derivative and Photolysis of Cobalt(III)?Trifluoromethyl Bond (2018)
  • Author(s): Ono Toshikazu、Wakiya Kosuke、Hossain Md. Jakir、Shimakoshi Hisashi、Hisaeda Yoshio
  • Journal Title: Chemistry Letters Volume: 47 Issue: 8 Pages: 979-981
  • DOI: 10.1246/cl.180355
  • NAID: 130007431003
  • Peer Reviewed / Open Access
• [Journal Article] Cobalt?Carbon Bond Formation Reaction via Ligand Reduction of Porphycene?Cobalt(II) Complex and Its Noninnocent Reactivity (2018)
  • Author(s): Koide Taro、Aritome Isao、Saeki Tatsuya、Morita Yoshitsugu、Shiota Yoshihito、Yoshizawa Kazunari、Shimakoshi Hisashi、Hisaeda Yoshio
  • Journal Title: ACS Omega Volume: 3 Issue: 4 Pages: 4027-4034
  • DOI: 10.1021/acsomega.8b00239
  • Peer Reviewed / Open Access
• [Journal Article] Learning from B12 enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis (2018)
  • Author(s): Tahara Keishiro、Pan Ling、Ono Toshikazu、Hisaeda Yoshio
  • Journal Title: Beilstein Journal of Organic Chemistry Volume: 14 Pages: 2553-2567
  • DOI: 10.3762/bjoc.14.232
  • Peer Reviewed
• [Journal Article] Switching of Monomer Fluorescence, Charge-Transfer Fluorescence, and Room-Temperature Phosphorescence Induced by Aromatic Guest Inclusion in a Supramolecular Host (Chem. Eur. J. 66/2018) (2018)
  • Author(s): Ono Toshikazu、Taema Ai、Goto Aiko、Hisaeda Yoshio
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 66 Pages: 17368-17368
  • DOI: 10.1002/chem.201805575
  • Peer Reviewed
• [Journal Article] Gram-scale synthesis of porphycenes through acid-catalyzed oxidative macrocyclizations of E/Z-mixed 5,6-diaryldipyrroethenes (2018)
  • Author(s): Toshikazu Ono, Ning Xu, Daiki Koga, Toshihiro Ideo, Manabu Sugimoto, Yoshio Hisaeda
  • Journal Title: RSC Adv. Volume: 8 Issue: 69 Pages: 39269-39273
  • DOI: 10.1039/c8ra09040h
  • Peer Reviewed / Open Access
• [Presentation] 生物無機化学を基盤とした環境化学への挑戦： 光および電気化学的に活性化するバイオインスパイアード触媒 (2019)
  • Author(s): 久枝良雄
  • Organizer: 福岡大学講演会2019
  • Invited
• [Presentation] バイオインスパイアード触媒 (2019)
  • Author(s): 久枝良雄
  • Organizer: CERI公開講座 「先端分子材料化学:設計、構造・物性、機能からデバイスまで」
  • Invited
• [Presentation] Bioinspired Catalytic System with Vitamin B12 Function (2018)
  • Author(s): Yoshio Hisaeda
  • Organizer: Conference on New Advances in the Chemistry of Porphyrinoids
  • Int'l Joint Research / Invited
• [Presentation] Facile Synthesis of Porphycene Derivatives and Reactivity of Cobalt Porphycene (2018)
  • Author(s): Yoshio Hisaeda
  • Organizer: 10th International Conference on Porphyrins & Phthalocyanines (ICPP-10)
  • Int'l Joint Research / Invited
• [Presentation] Electrochemical Perfluoroalkylation of Arenes and Heteroarenes Catalyzed by Vitamin B12 Derivative (2018)
  • Author(s): Y. Hisaeda, M. J. Hossain, T. Ono, H. Shimakoshi, H. Amii, D. Gryko
  • Organizer: International Conference on Coordination Chemistry (ICCC)
  • Int'l Joint Research
• [Presentation] Electrochemical Perfluoroalkylations of Arenes and Heteroarenes by Bioinspired Catalytic System (2018)
  • Author(s): Yoshio Hisaeda
  • Organizer: 13th International Symposium on Organic Reaction (ISOR-13)
  • Int'l Joint Research / Invited
• [Book] Advances in Bioorganometallic Chemistry (2019)
  • Author(s): H. Shimakoshi, Y. Hisaeda
  • Total Pages: 10
  • Publisher: Elsevier