新規不斉場を有する不斉有機分子触媒ライブラリーの構築

• Project Area: Advanced Molecular Transformations by Organocatalysts
• Project/Area Number: 26105702
• 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: Hokkaido University
• Principal Investigator: 小笠原 正道 北海道大学, 触媒科学研究所, 准教授 (70301231)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2015: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2014: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 面不斉 / 有機分子触媒 / フェロセン / ピリジン / 不斉合成 / ライブラリィ / ライブラリー

Outline of Annual Research Achievements

不斉合成反応において高いエナンチオ選択性を達成するためには「効果的なキラル・テンプレート」の設計が重要である。従来の不斉有機分子触媒において利用されている不斉源は、軸不斉ビアリール類を除けばほとんどが天然物由来であり、不斉触媒設計のバリエーションが限られているのが現状である。このような背景のもと、本研究では「新規な不斉有機分子触媒の設計と合成」および「既存の合成困難な不斉有機触媒分子の効率的合成法の開発」を基軸として、新規不斉場を有する不斉有機分子触媒ライブラリーの構築を目的とした。
平成２７年度の研究では、優れたルイス塩基性不斉有機分子触媒としてしられている、BINAP oxideの誘導体の合成と応用を行った。BINAP oxideのビナフチル骨格の４位および４’位に嵩高い置換基を導入すると、様々なルイス塩基触媒反応におけるエナンチオ選択性が劇的に向上することが見出された。中でも、置換基としてトリイソプロピルシリル基を導入した場合に最も高いエナンチオ選択性を示した。この４位および４’位は、触媒活性点であるホスフィンオキシド置換基からは一見離れた位置であり、この部位を立体修飾することによる選択性向上は、非常に興味深い知見である。また、こうして得られた修飾BINAP oxideを不斉有機分子触媒として用いて、天然物である(-)-ericanoneの不斉全合成を達成した。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Kinetic Resolution of Planar-Chiral Ferrocenylphosphine Derivatives by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis and Their Application in Asymmetric Catalysis (2016)
  • Author(s): Ogasawara, M.; Arae, S.; Watanabe, S.; Nakajima, K.; Takahashi, T.
  • Journal Title: ACS Catal. Volume: 6 Issue: 2 Pages: 1308-1315
  • DOI: 10.1021/acscatal.5b02692
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Concise Asymmetric Construction of C2-Symmetric 1,9-Diarylnonanoids Using Hypervalent Silicon Complex: Total Synthesis of (-)-Ericanone (2016)
  • Author(s): Kotani, S.; Kai, K.; Shimoda, Y.; Hu, H.; Gao, S.; Sugiura, M.; Ogasawara, M.; Nakajima, M.
  • Journal Title: Chem. Asian J. Volume: 11 Issue: 3 Pages: 376-379
  • DOI: 10.1002/asia.201501080
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Enantioselective Synthesis of Macrocyclic Heterobiaryl Derivatives by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis Inducing Winding Vine-Shaped Molecular Asymmetry (2015)
  • Author(s): Y. Okayama, S. Tsuji, Y. Toyomori, T. Mori, S. Arae, W.-Y. Wu, T. Takahashi, M. Ogasawara
  • Journal Title: Angewandte Chemie International Edition Volume: 54 Issue: 16 Pages: 4927-4931
  • DOI: 10.1002/anie.201500459
  • Peer Reviewed
• [Journal Article] Enantioselective Desymmetrization of 1, 2, 3-Trisubstituted Metallocenes by Molybdenum-Catalyzed Asymmetric Intraannular Ring-Closing Metathesis (2015)
  • Author(s): S. Arae, K. Nakajima, T. Takahashi, M. Ogasawara
  • Journal Title: Organometallics Volume: 34 Issue: 7 Pages: 1197-1202
  • DOI: 10.1021/om5011484
  • Peer Reviewed
• [Journal Article] Enantioselective Synthesis of Planar-Chiral Ferrocene-Fused 4-Pyridones and Their Application in Construction of Pyridine-Based Organocatalyst Library (2015)
  • Author(s): Masamichi Ogasawara, Shiro Wada, Erika Isshiki, Takumi Kamimura, Akira Yanagisawa, Tamotsu Takahashi, Kazuhiro Yoshida
  • Journal Title: Org. Lett. Volume: 17 Issue: 9 Pages: 2286-2289
  • DOI: 10.1021/acs.orglett.5b01044
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Ring-Closing Metathesis of (η5-Alkenylcyclopentadienyl)(alkenylphosphine)manganese(I) Dicarbonyl Complexes (2015)
  • Author(s): Tseng, Y.-Y.; Kamikawa, K.; Wu, Q.; Takahashi, T.; Ogasawara, M.
  • Journal Title: Adv. Synth. Catal. Volume: 357 Issue: 10 Pages: 2255-2264
  • DOI: 10.1002/adsc.201500343
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Simultaneous Induction of Axial and Planar-Chirality in Arene-Chromium Complexes by Molybdenum-Catalyzed Enantioselective Ring-Closing Metathesis (2015)
  • Author(s): K. Kamikawa, S. Arae, W.-Y. Wu, C. Nakamura, T. Takahashi, M. Ogasawara
  • Journal Title: Chemistry-A European Journal Volume: 21 Issue: 13 Pages: 4954-4957
  • DOI: 10.1002/chem.201500226
  • Peer Reviewed
• [Journal Article] Hybrid sponge comprised of galactosylated chitosan and hyaluronic acid mediates the co-culture of hepatocytes and endothelial cells (2014)
  • Author(s): Shang, Y., M. Tamai, R. Ishii, N. Nagaoka, Y. Yoshida, M. Ogasawara, J. Yang, Y. Tagawa
  • Journal Title: J. Biosci. Bioeng. Volume: 117 Issue: 1 Pages: 99-106
  • DOI: 10.1016/j.jbiosc.2013.06.015
  • Peer Reviewed
• [Journal Article] Phosphine-Olefin Ligands Based on a Planar-Chiral(π-Arene)chromium Scaffold : Design, Synthesis, and Application in Asymmetric Catalysis (2014)
  • Author(s): M. Ogasawara, Y.-Y. Tseng, S. Arae, T. Morita, T. Nakaya, W.-Y. Wu, T. Takahashi, K. Kamikawa
  • Journal Title: the Journal of the American Chemical Society Volume: 136 Issue: 26 Pages: 9377-9384
  • DOI: 10.1021/ja503060e
  • Peer Reviewed
• [Journal Article] Phosphine Oxide-Catalyzed Enantioselective Intramolecular Aldol Reaction via Regioselective Enolization of Unsymmetrical Diketones with Tetrachlorosilane (2014)
  • Author(s): Kotani, S.; Aoki, S.; Sugiura, M.; Ogasawara, M.; Nakajima, M.
  • Journal Title: Org. Lett. Volume: 16 Issue: 18 Pages: 4802-4805
  • DOI: 10.1021/ol502269w
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Catalytic Asymmetric Synthesis of Planar-Chiral Zirconocene Derivatives and Their Application in Carbometallation Reactions (2016)
  • Author(s): Masamichi Ogasawara
  • Organizer: Pure and Applied Chemistry International Conference 2016 (PACCON 2016)
  • Place of Presentation: Bangkok, Thailand
  • Year and Date: 2016-02-09
  • Int'l Joint Research / Invited
• [Presentation] Catalytic Enantioselective Synthesis of Planar-Chiral Zirconocenes and Application in Asymmetric Catalysis (2015)
  • Author(s): Masamichi Ogasawara
  • Organizer: International Science & Nature Congress (ISNaC2015)
  • Place of Presentation: Kuala Lumpur, Malaysia
  • Year and Date: 2015-09-21
  • Int'l Joint Research / Invited
• [Presentation] 面不斉遷移金属錯体の触媒的不斉合成と有機合成反応への応用 (2015)
  • Author(s): 小笠原正道
  • Organizer: Symposium on Molecular Chirality
  • Place of Presentation: 早稲田大学（東京都新宿区）
  • Year and Date: 2015-06-12
  • Invited
• [Presentation] Design, Synthesis, and Application of Atropisomeric Chiral Dienes in Asymmetric Catalysis (2014)
  • Author(s): Masamichi Ogasawara
  • Organizer: The 8th Singapore International Chemical Conference (SICC8)
  • Place of Presentation: Singapore (Singapore)
  • Year and Date: 2014-12-14 – 2014-12-17
  • Invited
• [Presentation] 均一系遷移金属触媒による非中心不斉の立体制御 (2014)
  • Author(s): 小笠原正道
  • Organizer: オルガノメタリックセミナー
  • Place of Presentation: 東京農工大学（東京都小金井市）
  • Year and Date: 2014-11-25
  • Invited
• [Presentation] Enantioselective Synthesis of Planar-Chiral Ferrocene-Fused 4-Pyridones and Their Application in Construction of Pyridine-Based Organocatalyst Library (2014)
  • Author(s): Masamichi Ogasawara
  • Organizer: Vietnam Malaysia International Chemical Conference
  • Place of Presentation: Hanoi (Vietnam)
  • Year and Date: 2014-11-07 – 2014-11-09
  • Invited
• [Presentation] Development of Enantioselective Transformations on (η6-Arene)chromium Templates by Molybdenum-Catalyzed Asymmetric Metathesis Reactions (2014)
  • Author(s): Masamichi Ogasawara
  • Organizer: The 18th Malaysian International Chemical Congress
  • Place of Presentation: Kuala Lumpur (Malaysia)
  • Year and Date: 2014-11-03 – 2014-11-05
  • Invited
• [Presentation] Catalytic Enantioselective Synthesis of Planar-Chiral Transition-Metal Complexes and Their Application in Organic Transformations (2014)
  • Author(s): Masamichi Ogasawara
  • Organizer: The 8th Asian European Symposium on Metal-Mediated Efficient Organic Synthesis (8th AES-MMEOS)
  • Place of Presentation: Izmir (Turkey)
  • Year and Date: 2014-09-07 – 2014-09-10
  • Invited
• [Presentation] Development of Catalytic Enantioselective Transformations Utilizing (η6-Arene)chromium Templates and Chiral Molybdenum-Alkylidene Catalysts (2014)
  • Author(s): Masamichi Ogasawara
  • Organizer: 41st International Conference on Coordination Chemistry (ICCC-41)
  • Place of Presentation: Singapore (Singapore)
  • Year and Date: 2014-07-21 – 2014-07-25
  • Invited