Catalytic Asymmetric Synthesis of Phosphine Derivatives with a Stereogenic Phosphorus Atom

• Project/Area Number: 26620074
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: OGASAWARA Masamichi 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: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2014: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 触媒的不斉合成 / リン / 中心不斉 / メタセシス / 非対称化 / モリブデン / クロム / 不斉合成 / ホスフィン / 閉環メタセシス

Outline of Final Research Achievements

We have achieved the formal asymmetric cross-metathesis between an alkenylbenzene derivative and a bis(methallyl)phosphine by the use of a chiral molybdenum-alkylidene catalyst giving the phosphine drivative with a stereogenic phosphorus atom in up to 95% ee. Our strategy is the use of a chromium fragment as a template, in which the two reactants are preinstalled onto the chromium metal. The chromium complexes thus obtained were employed as substrates for the asymmetric ring-closing metathesis and the subsequent de-chromation reaction afforded the acyclic metal-free phosphine derivatives with the perfect chemo-selectivity and the Z-selectivity.

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] メタセシス反応による面不斉遷移金属錯体の触媒的不斉合成 (2016)
  • Author(s): 小笠原正道
  • Journal Title: ファインケミカル Volume: 45 Pages: 15-23
  • Peer Reviewed
• [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 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] 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] 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] Catalytic Asymmetric Synthesis of Planar-Chiral Transition-Metal Complexes (2012)
  • Author(s): 荒江祥永・小笠原正道
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 70 Issue: 6 Pages: 593-605
  • DOI: 10.5059/yukigoseikyokaishi.70.593
  • NAID: 10030765844
  • ISSN: 0037-9980, 1883-6526
  • Peer Reviewed
• [Presentation] Catalytic Asymmetric Synthesis of Planar-Chiral Zirconocene Derivatives and Their Application in Carbometallation Reactions (2016)
  • Author(s): Masamichi Ogasawara
  • Organizer: ure 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 P-Stereogenic Phosphine Derivatives by Mo-Catalyzed Asymmetric Ring-Closing Metathesis on (π-Arene)chromium Platform (2015)
  • Author(s): Masamichi Ogasawara, Ryohsuke Ikehata, Ya-Yi Tseng, Wei-Yi Wu, Rie Takahashi, Sachie Arae, Tamotsu Takahashi, Ken Kamikawa
  • Organizer: IKCOC-2015
  • Place of Presentation: リーガロイヤルホテル（京都市）
  • Year and Date: 2015-11-09
  • Int'l Joint Research
• [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] 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
• [Patent(Industrial Property Rights)] 面不斉シクロペンタジエニル―マンガン錯体を基本骨格に有するホスフィン―オレフィン配位子 (2015)
  • Inventor(s): 神川 憲・チェン ヤーイー・小笠原正道・高橋 保
  • Industrial Property Rights Holder: 神川 憲・チェン ヤーイー・小笠原正道・高橋 保
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2015-128291
  • Filing Date: 2015-06-26