Development of multifunctional asymmetric catalysts based on chirality control and integration of oxo-metal complex

• Project Area: Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
• Project/Area Number: 17H05373
• 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: Osaka University
• Principal Investigator: 滝澤 忍 大阪大学, 産業科学研究所, 准教授 (50324851)
• Project Period (FY): 2017-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2018: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2017: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: オキソバナジウム / 中心性キラリティー / キラルLewis酸 / 一電子移動型高次機能集合体 / 集積化・非集積化 / ホモカップリング / ヘテロカップリング / ヘリカル集積体 / キラル / バナジウム / 不斉触媒 / 酸化 / 集積 / 二核 / 単核 / 不斉カップリング / BINOL / sorazolon E2 / カルバゾール / 二重活性化 / 触媒・化学プロセス / 分子認識 / 自己組織化 / 超分子化学 / イオン結晶

Outline of Annual Research Achievements

本研究では、高酸化状態にあるオキソバナジウム金属自身に中心性キラリティーを導入し、集積化することで、キラルLewis酸・一電子移動型高次機能集合体として働く、新規多機能不斉触媒を創製を目指した。具体的には、1) キラル金属錯体集積化・非集積化による両鏡像異性体の作り分け、2) キラル金属錯体集積化による触媒活性と位置選択性の改善、3) キラル金属錯体集積化・非集積化を基盤とするラジカルホモカップリング、及び、ラジカルアニオンヘテロカップリング反応の開発、4) 有機分子触媒との集積化を基盤とする新規多機能不斉触媒の創製、5) 本申請研究で開発した触媒とアルカリ金属を混合することで生成するヘリカル集積体構造の解析とその固定化不斉触媒としての評価、以上5つの項目について検討を行った。ラセミ化しやすいテトラヘドラル構造を有するオキソバナジウム錯体を、キラル平面環状多座配位子を用いることで強固なオクタヘドラル構造に固定することで、バナジウム金属自身の中心性キラリティーは安定化する。その結果、レゾルシノール、及び、ヒドロキシカルバゾールのホモカップリング反応においてバナジウム錯体のキラリティーを様々な対応するカップリング生成物に効率的に不斉転写できた。また、キラルバナジウム金属錯体集積化・非集積化によるBINOL誘導体の両鏡像異性体の作り分けにも成功した。この成果は韓国中央大学薬学部のOh教授との共同研究によるものである。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Bielefeld University(ドイツ)
• [Int'l Joint Research] Chung-Ang University(韓国)
• [Int'l Joint Research] パリ南大学(フランス)
• [Int'l Joint Research] 中央大学(韓国)
• [Journal Article] 2.Chiral Dinuclear Vanadium Complex-mediated Oxidative Coupling of Resorcinols (2019)
  • Author(s): Makoto Sako, Takanori Aoki, Nadine Zumbrägel, Lukas Schober, Harald Gröger, Shinobu Takizawa, Hiroaki Sasai
  • Journal Title: J. Org. Chem. Volume: 84 Issue: 3 Pages: 580-1587
  • DOI: 10.1021/acs.joc.8b02494
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Chiral Vanadium Complex-catalyzed Enantioselective Oxidative Coupling Reactions (2018)
  • Author(s): Sako Makoto、Takizawa Shinobu、Sasai Hiroaki
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 76 Issue: 9 Pages: 874-884
  • DOI: 10.5059/yukigoseikyokaishi.76.874
  • NAID: 130007472395
  • ISSN: 0037-9980, 1883-6526
  • Year and Date: 2018-09-01
  • Peer Reviewed
• [Journal Article] Asymmetric oxidative coupling of hydroxycarbazoles: Facile synthesis of (+)-bi-2-hydroxy-3-methylcarbazole (2018)
  • Author(s): Sako Makoto、Sugizaki Akimasa、Takizawa Shinobu
  • Journal Title: Bioorg. Med. Chem. Lett Volume: - Issue: 16 Pages: 2751-2753
  • DOI: 10.1016/j.bmcl.2018.02.033
  • Peer Reviewed
• [Journal Article] Vanadium-Catalyzed Dehydrogenation of N-Heterocycles in Water (2018)
  • Author(s): Zumbragel Nadine、Sako Makoto、Takizawa Shinobu、Sasai Hiroaki、Groger Harald
  • Journal Title: Organic Letters Volume: 20 Issue: 16 Pages: 4723-4727
  • DOI: 10.1021/acs.orglett.8b01484
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Enantioselective synthesis of spiro (isoxazole-isoxazoline) hybrid ligands (2018)
  • Author(s): B. M. Chaki, K. Wakita, S. Takizawa, K. Takenaka, H. Sasai
  • Journal Title: Heterocycles Volume: - Issue: 1 Pages: 493-505
  • DOI: 10.3987/com-18-s(t)41
  • Peer Reviewed
• [Journal Article] Enantio- and Diastereoselective Betti/aza-Michael Sequence: Single Operated Preparation of Chiral 1,3-Disubstituted Isoindolines (2017)
  • Author(s): Takizawa Shinobu、Sako Makoto、Abozeid Mohamed Ahmed、Kishi Kenta、Wathsala H. D. P.、Hirata Shuichi、Murai Kenichi、Fujioka Hiromichi、Sasai Hiroaki
  • Journal Title: Organic Letters Volume: 19 Issue: 19 Pages: 5426-5429
  • DOI: 10.1021/acs.orglett.7b02693
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Chiral Organocatalyzed Intermolecular Rauhut–Currier Reaction of Nitroalkenes with Ethyl Allenoate (2017)
  • Author(s): S. Takizawa, M. Sako, K. Kishi, M. Shigenobu, G. Vo-Thanh, H. Sasai
  • Journal Title: Chemical and Pharmaceutical Bulletin Volume: 65 Issue: 11 Pages: 997-999
  • DOI: 10.1248/cpb.c17-00554
  • NAID: 130006191501
  • ISSN: 0009-2363, 1347-5223
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Reversal of Enantioselectivity Approach to BINOLs via Single and Dual 2-Naphthol Activation Modes (2017)
  • Author(s): Kim Hun Young、Takizawa Shinobu、Sasai Hiroaki、Oh Kyungsoo
  • Journal Title: Organic Letters Volume: 19 Issue: 14 Pages: 3867-3870
  • DOI: 10.1021/acs.orglett.7b01734
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Short syntheses of 4-deoxycarbazomycin B, sorazolon E, and (+)-sorazolon E2 (2017)
  • Author(s): M. Sako, K. Ichinose, S. Takizawa, H. Sasai
  • Journal Title: Chem. Asian J. Volume: 12 Issue: 12 Pages: 1305-1308
  • DOI: 10.1002/asia.201700471
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Determination of the absolute configuration of compounds bearing chiral quaternary carbon centers using the crystalline sponge method (2017)
  • Author(s): Sairenji Shiho、Kikuchi Takashi、Abozeid Mohamed Ahmed、Takizawa Shinobu、Sasai Hiroaki、Ando Yuichiro、Ohmatsu Kohsuke、Ooi Takashi、Fujita Makoto
  • Journal Title: Chem. Sci. Volume: 8 Issue: 7 Pages: 5132-5136
  • DOI: 10.1039/c7sc01524k
  • Peer Reviewed / Open Access
• [Journal Article] Enantioselective synthesis of tetrahydrocyclopenta[b]indole bearing a chiral quaternary carbon center via Pd(ii)?SPRIX-catalyzed C?H activation (2017)
  • Author(s): Abozeid Mohamed Ahmed、Sairenji Shiho、Takizawa Shinobu、Fujita Makoto、Sasai Hiroaki
  • Journal Title: Chemical Communications Volume: 53 Issue: 51 Pages: 6887-6890
  • DOI: 10.1039/c7cc03199h
  • Peer Reviewed
• [Journal Article] Multifunctional catalysis: stereoselective construction of α-methylidene-γ-lactams via an amidation/Rauhut?Currier sequence (2017)
  • Author(s): Kishi Kenta、Arteaga Fernando Arteaga、Takizawa Shinobu、Sasai Hiroaki
  • Journal Title: Chemical Communications Volume: 53 Issue: 55 Pages: 7724-7727
  • DOI: 10.1039/c7cc02839c
  • Peer Reviewed / Int'l Joint Research
• [Presentation] グリーンケミストリー志向型不斉合成反応の開発と多官能性複素環骨格構築への応用 (2019)
  • Author(s): 滝澤忍
  • Organizer: 日本薬学会第139年会
  • Invited
• [Presentation] Enantioselective domino processes mediated by multifunctional catalysts -Towards environmentally benign asymmetric synthesis- (2019)
  • Author(s): S. Takizawa
  • Organizer: The 5th International Symposium toward the Future of Advanced Researches in Shizuoka University 2019
  • Int'l Joint Research / Invited
• [Presentation] Vanadium Complex-catalyzed Enantioselective Synthesis of Oxa[9]helicenes (2018)
  • Author(s): Sako, M.; Takizawa, S.; Sasai, H.
  • Organizer: IRCCS-JST CREST Joint Symposium
  • Int'l Joint Research
• [Presentation] Enantioselective C-C Bond Forming Reactions Catalyzed by a Vanadium Complex (2018)
  • Author(s): Sako, M.; Aoki, T.; Sugizaki, A.; Tamori, Y.; Takizawa, S.; Sasai, H.
  • Organizer: IRCCS-JST CREST Joint Symposium
  • Int'l Joint Research
• [Presentation] Chiral Vanadium Complex-catalyzed Enantioselective Oxidative Coupling Reactions of Polycyclic Phenol (2018)
  • Author(s): Sugizaki, A.; Sako, M.; Takizawa, S.; Sasai, H.
  • Organizer: Biotechnology and Chemistry for Green Growth (JSPS Japanese-German Graduate Externship Program)
  • Int'l Joint Research
• [Presentation] Chiral Dinuclear Vanadium Complex-mediated Oxidative Coupling of Monocyclic Phenols (2018)
  • Author(s): Sako, M.; Aoki, T.; Takizawa, S.; Sasai, H.
  • Organizer: 43rd International Conference on Coordination Chemistry (ICCC 2018)
  • Int'l Joint Research
• [Presentation] Enantioselective Oxidative C-H/C-H Coupling Catalyzed by Chiral Dinuclear Vanadium(V) Complex (2018)
  • Author(s): Sako, M.; Aoki, T.; Takizawa, S.; Sasai, H.
  • Organizer: The 4th International Symposium on C-H Activation (ISCHA4)
• [Presentation] Vanadium(V) Complex-catalyzed Oxidative Hetero-coupling Reactions (2018)
  • Author(s): Jiang, Y.; Sako, M.; Takizawa, S.; Sasai, H.
  • Organizer: Biotechnology and Chemistry for Green Growth (JSPS Japanese-German Graduate Externship Program)
• [Presentation] Chiral Dinuclear Vanadium Complex-mediated Oxidative Coupling of Phenols (2018)
  • Author(s): Sako, M.; Aoki, T.; Takizawa, S.; Sasai, H.
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-14)
• [Presentation] Catalytic Enantioselective Sequential C-C Bond Forming Reactions in Flow System (2018)
  • Author(s): Wathsala, H. D. P.; Kishi, K.; Chen, Q.; Sako, M.; Takizawa, S.; Sasai, H.
  • Organizer: 21st SANKEN International Symposium
  • Int'l Joint Research
• [Presentation] Catalytic Enantioselective Sequential C-C Bond Forming Reactions in Flow System (2018)
  • Author(s): Wathsala, H. D. P.; Kishi K.; Chen, Q.;Takizawa, S.; Sasai, H.
  • Organizer: The First International Conference on Automated Flow and Microreactor Synthesis (ICAMS-1)
  • Int'l Joint Research
• [Presentation] Facile Synthesis of Spirooxindoles via Enantioselective Double Michael Reaction (2018)
  • Author(s): Kusaba, M.; Kishi, K.; Takizawa, S.; Bai, J.; Sasai, H.
  • Organizer: Biotechnology and Chemistry for Green Growth
  • Int'l Joint Research
• [Presentation] Enantioselective carbon-carbon bond-forming reactions catalyzed by vanadium(V) complexes (2017)
  • Author(s): S. Takizawa, M. Sako, H. Sasai
  • Organizer: Korean Chemical Society 120th General Meetings
  • Int'l Joint Research / Invited
• [Book] 有機分子触媒の開発と工業利用 (2018)
  • Author(s): 笹井宏明、滝澤忍
  • Total Pages: 330
  • Publisher: シーエムシー出版
  • ISBN: 9784781313238
• [Book] 化学工業 (2017)
  • Author(s): 滝澤忍、笹井宏明
  • Total Pages: 80
  • Publisher: 化学工業社
• [Remarks] 大阪大学産業科学研究所 機能物質化学研究分野
  • URL: https://www.sanken.osaka-u.ac.jp/labs/soc/socmain.html
• [Remarks] 大阪大学産業科学研究所機能物質化学研究分野ホームページ
  • URL: http://www.sanken.osaka-u.ac.jp/labs/soc/socmain.html