Catalytic Asymmetric Synthesis of Chiral Transition-Metal Complexes by the Use of Modern Organic Transformation

2013 Fiscal Year Final Research Report

• Project/Area Number: 24655039
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Single-year Grants
• Research Field: Inorganic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: OGASAWARA Masamichi 北海道大学, 触媒化学研究センター, 准教授 (70301231)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Keywords: 有機金属化学 / 触媒的不斉合成 / 均一系触媒 / 面不斉 / メタロセン / アレーンクロム / メタセシス

Research Abstract

Kinetic resolution of 1,2-diallylferrocene derivatives by Mo-catalyzed asymmetric ring-closing metathesis (ARCM) gave the corresponding (4,7-dihydroindenyl)iron(II) derivatives in good yields with high enantioselectivity. In the same way, desymmetrization of (1,2,3-triallylindenyl)-metallocenes by ARCM provided the corresponding (1,4-dihydrofluorenyl)-metallocene derivatives in high ee's.
The Cs-symmetric zirconocenes could be converted to the corresponding C3-bridged planar-chiral ansa-zirconocenes by ARCM with high enantioselectivity. The obtained planar-chiral ansa-zirconocene complexes could be applicable to the asymmetric carbometallation reaction as catalysts.
Kinetic resolution of the racemic planar-chiral (arene)chromium complexes was realized by Mo-catalyzed ARCM with excellent enantioselectivity. The optically active (bromoarene)chromium complex thus obtained is an excellent precursor to various planar-chiral (arene)chromium complexes.

Research Products

• [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.; Tamai, M.; Ishii R.; Nagaoka, N.; Yoshida, Y.; Ogasawara, M.; Yang, J.; Tagawa, Y
  • Journal Title: J. Biosci. Bioeng Volume: 117 Pages: 99-106
  • DOI: 10.1016/j.jbiosc.2013.06.015
  • Peer Reviewed
• [Journal Article] Atropisomeric Chiral Dienes in Asymmetric Catalysis : C_2-Symmetric (Z,Z)-2,3-Bis[1-(di- phenylphosphinyl)ethylidene]tetralin as Highly Active Lewis-Base Organocatalyst (2013)
  • Author(s): Ogasawara, M.; Kotani, S.; Nakajima, H.; Furusho, H.; Miyasaka, M.; Shimoda, Y.; Wu, W.-Y.; Sugiura, M.; Takahashi, T.; Nakajima, M
  • Journal Title: Angew. Chem. Int. Ed. Volume: 52 Pages: 13798-13802
  • DOI: 10.1002/anie.201308112
  • Peer Reviewed
• [Journal Article] Asymmetric Aldol Reaction on Water using an Organocatalyst Tethered on a Thermoresponsive Block Copolymer (2013)
  • Author(s): Suzuki, N.; Inoue, T.; Asada, T.; Akebi, R. Kobayashi, G.; Rikukawa, M.; Masuyama, Y.; Ogasawara, M.; Takahashi, T.; Thang, S
  • Journal Title: Chem. Lett. Volume: 42 Pages: 1493-1495
  • DOI: 10.1246/cl.130711
  • Peer Reviewed
• [Journal Article] Inter- versus Intraannular Ring-Closing Metathesis on Polyallylferrocenes : Five-Fold RCM within a Single Molecule (2013)
  • Author(s): Ogasawara, M.; Wu, W.-Y.; Arae, S.; Nakajima, K.; Takahashi, T
  • Journal Title: Organometallics Volume: 32 Pages: 6593-6598
  • DOI: 10.1021/om400936b
  • Peer Reviewed
• [Journal Article] Enantioselective Morita-Baylis-Hillman Reaction Catalyzed by a Chiral Phosphine Oxide (2013)
  • Author(s): Kotani, S.; Ito, M.; Nozaki, H.; Sugiura, M.; Ogasawara, M.; Nakajima, M
  • Journal Title: Tetrahedron Lett. Volume: 54 Pages: 6430-6433
  • DOI: 10.1016/j.tetlet.2013.09.067
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Benzo[b]- phosphaferrocene Derivatives (2013)
  • Author(s): Ogasawara, M.; Arae, S.; Watanabe, S.; Subbarayan, V.; Sato, H.; Takahashi, T
  • Journal Title: Organometallics Volume: 32 Pages: 4997-5000
  • DOI: 10.1021/om400496b
  • Peer Reviewed
• [Journal Article] Kinetic Resolution of Planar-Chiral 1,2-Disubstituted Ferrocenes by Molybdenum-Catalyzed Asymmetric Intraannular Ring-Closing Metathesis (2013)
  • Author(s): Ogasawara, M.; Arae, S.; Watanabe, S.; Nakajima, K.; Takahashi, T
  • Journal Title: Chem. Eur. J. Volume: 19 Pages: 4151-4154
  • DOI: 10.1002/chem.201300116
  • Peer Reviewed
• [Journal Article] Preparation of C_2-Symmetric Allenes by Palladium-Catalyzed Double Nucleophilic Substitution on 3-Bromopenta-2,4-dienyl Acetate (2012)
  • Author(s): Ogasawara, M.; Suzuki, M.; Takahashi, T
  • Journal Title: J. Org. Chem. Volume: 77 Pages: 5406-5410
  • DOI: 10.1021/jo300511e
  • Peer Reviewed
• [Journal Article] Kinetic Resolution of Planar-Chiral (η^6-Arene)chromium Complexes by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis (2012)
  • Author(s): O gasawara, M. ; Wu, W.-Y.; Arae, S.; Watanabe, S.; Morita, T.; Takahashi, T.; Kamikawa, K
  • Journal Title: Angew. Chem. Int. Ed. Volume: 51 Pages: 2951-2955
  • DOI: 10.1002/anie.201108292
  • Peer Reviewed
• [Journal Article] Effects of Silyl Substituents on the Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral (Allenylmethyl)silanes and Their S_E2' Chirality Transfer Reactions (2012)
  • Author(s): Ogasawara, M.; Ge, Y.; Okada, A.; Takahashi, T
  • Journal Title: Eur. J. Org. Chem. Pages: 1656-1663
  • DOI: 10.1002/ejoc.201101634
  • Peer Reviewed
• [Journal Article] 面不斉遷移金属錯体の触媒的不斉合成 (2012)
  • Author(s): 荒江祥永・小笠原正道
  • Journal Title: 有機合成化学協会誌 Volume: 70 Pages: 593-605
  • DOI: 10.5059/yukigoseikyokaishi.70.593
  • Peer Reviewed
• [Presentation] Catalytic Enantioselective Synthesis of Planar-Chiral (η^6-Arene)chromium Complexes (2014)
  • Author(s): Ogasawara, M.
  • Organizer: The 247th ACS National Meeting, Dallas
  • Place of Presentation: TX, USA
  • Year and Date: 20140316-20
• [Presentation] Atropisomeric Chiral Dienes in Asymmetric Catalysis : Design, Synthesis, and Application of C_2-Symmetric (Z,Z)-1,2-Bis[1-(diphenylphosphino)ethylidene]c ycloalkane Derivatives (2013)
  • Author(s): Ogasawara, M.
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2013 (C&FC 2013)
  • Place of Presentation: Renmin University of China, Beijing, China
  • Year and Date: 20131201-05
• [Presentation] 新規不斉有機分子触媒ライブラリーの構築 (2013)
  • Author(s): 小笠原正道
  • Organizer: 日本プロセス化学会2013ウインターシンポジウム
  • Place of Presentation: 日本プロセス化学会、仙台市民会館(仙台市)
  • Year and Date: 20131128-29
• [Presentation] Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral Allenes and Application to Synthesis of Allenic Natural Products (2013)
  • Author(s): Ogasawara, M.
  • Organizer: The 48th Advances in Organic, Bioorganic and Pharmaceutical Chemistry (Liblice 2013)
  • Place of Presentation: Harmony Hotel,Špindlerův Mlýn, Czech Republic
  • Year and Date: 20131101-03
• [Presentation] Catalytic Enantioselective Synthesis of Planar-Chiral (π-Arene)chromium Complexes (2013)
  • Author(s): Ogasawara, M
  • Organizer: The 4th UK/Japan Conference in Catalytic Asymmetric Synthesis
  • Place of Presentation: Sendai International Center, Sendai, Japan
  • Year and Date: 20130418-21
• [Presentation] Catalytic Enantioselective Synthesis of Planar-Chiral Transition-Metal Complexes (2013)
  • Author(s): Ogasawara, M
  • Organizer: The 245th ACS National Meeting
  • Place of Presentation: The 245th ACS National Meeting
  • Year and Date: 20130407-11
• [Presentation] Catalytic Asymmetric Synthesis of Planar-Chiral Ferrocenes and Their Applications in Optically Active Metallocene-Polymers (2013)
  • Author(s): Ogasawara, M
  • Organizer: The 3rd Molecular Materials Meeting (M3)
  • Place of Presentation: Singapore, Singapore
  • Year and Date: 20130114-16
• [Presentation] (2012)
  • Author(s): Ogasawara, M
  • Organizer: Visiting Lecturer of the Chemistry Research Promotion Center (Taiwan)
  • Place of Presentation: National Science Council, Taiwan
  • Year and Date: 20121224-28
• [Presentation] Herically Chiral Dienes in Asymmetric Catalysis : C_2-Symmetric (Z, Z)-1,2-Bis(1-diphenylphosphinylethylidene)cyclo hexanes as Highly Acitve Lewis-Base Organocatalysts (2012)
  • Author(s): Ogasawara, M
  • Organizer: The 1st Japan-USA Organocatalytic Symposium
  • Place of Presentation: Honolulu, HI, USA
  • Year and Date: 20121215-18
• [Presentation] Design and Synthesis of Phosphine-Olefin Ligands Having Planar-Chiral (π-Arene)chromium Framework and Application in Asymmetric Catalysis (2012)
  • Author(s): Ogasawara, M
  • Organizer: Cambodian Malaysian Chemical Conference
  • Place of Presentation: Siem Reap, Cambodia
  • Year and Date: 20121019-21
• [Presentation] Helically Chiral Dienes in Asymmetric Catalysis : Design, Synthesis, and Application of 1,4-Bis(phosphino)-1,3-butadiene Derivatives Having C2-C3-Fused Cyclic System (2012)
  • Author(s): Ogasawara, M
  • Organizer: The 17th Malaysian Chemical Congress
  • Place of Presentation: Kuala Lumpur, Malaysia
  • Year and Date: 20121015-17