Synthetic Chemistry of Allenic Compounds Catalyzed/Mediated by Transition-Metal Species

• Project/Area Number: 24350044
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic 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 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000); Fiscal Year 2014: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000); Fiscal Year 2013: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000); Fiscal Year 2012: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000)
• Keywords: アレン / 遷移金属触媒 / 軸不斉 / 天然物 / 不斉合成 / 均一系触媒 / パラジウム / 全合成 / 薬理活性 / ビススルホン / 不斉転写

Outline of Final Research Achievements

Synthetic chemistry of allenic compounds, which are important synthones in organic chemistry, has been developed using various transition-metal speceis. It was found that the use of BDT, which is a cyclic bissulfone, as a pronucleophile in the palladium-catalyzed allene synthesis reaction afforded the corresponding axially chiral allenes in high yields with excellent enantioselectivity. This novel reaction conditions enabled us to access various alkyl-substituted allenes, and thus the asymmetric total synthesis of a wide range of naturally occurring allenes could be realized.
Easily accessible 3-bromopenta-2,4-dienyl acetate was applied to the palladium-catalyzed reaction with soft nucleophiles. The reaction proceeded through the stepwise twofold nucleophilic substitution via formal SN2'- and SN2-processes giving the various doubly functionalized C2-symmetric allenes in good yields.

Research Products

• [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 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] Catalytic Asymmetric Synthesis of Planar-Chiral Transition-Metal Complexes (2015)
  • Author(s): S. Arae, M. Ogasawara
  • Journal Title: Tetrahedron Letters Volume: 56 Issue: 14 Pages: 1751-1761
  • DOI: 10.1016/j.tetlet.2015.01.130
  • 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
• [Journal Article] Kioetio Resolution of Planar-Chiral,1,2-Disuhsrituted Fetroones by Molybdenum-Caralyzed Asymmetric Iutraanular Ring-Cloeing Metafhesis (2013)
  • Author(s): Masamichi Ogasawara, Sachie Arae, Susumu Watanabe, Kiyohiko Nakajima, Tamotsu Takahashi
  • Journal Title: Chemistry-A European Journel Volume: 19 Issue: 13 Pages: 4151-4154
  • DOI: 10.1002/chem.201300116
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Benzo[b]phosphaferrocene Derivatives (2013)
  • Author(s): Ogasawara, Masamichi; Arae, Sachie; Watanabe, Susumu; Subbarayan, Velusamy; Sato, Hiroyasu; Takahashi, Tamotsu
  • Journal Title: Organometallics Volume: 32(17) Issue: 17 Pages: 4997-5000
  • DOI: 10.1021/om400496b
  • Peer Reviewed
• [Journal Article] Inter-versus Intraanular-Ring-Closing Metathesis of Polyallylferrocenes Ftye-Fold RCM within a Single Molecole (2013)
  • Author(s): Masamichi Ogasawara, Wei-Yi Wu, Sachie Arae, Kiyohiko Nakajima, Tamotsu Takahashi
  • Journal Title: Organometallics Volume: 32 Issue: 21 Pages: 6593-6598
  • DOI: 10.1021/om400936b
  • Peer Reviewed
• [Journal Article] Helically Chiral Diene in Asymmetric Catalysis: C2-Symmetric (Z,Z)-2,3-Bis[1-(diphenylphosphinyl)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: Angewandte Chemie International Edition Volume: 52 Issue: 51 Pages: 13798-13802
  • DOI: 10.1002/anie.201308112
  • Peer Reviewed
• [Journal Article] Effects of Silyl Substituents on the Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral (Allenylmethy1)silanes and Their SE2 Chirality Transfer Reactions (2012)
  • Author(s): 小笠原正道
  • Journal Title: European Journal of Organic Chemistry Volume: 2012 Issue: 8 Pages: 1656-1663
  • DOI: 10.1002/ejoc.201101634
  • Peer Reviewed
• [Journal Article] Preparation of C2-Symmetric Allenes by Palladium-Catalyzed Double-Nucleophilic Substitution on 3-Bromopenta-2,4-dienyl Acetate (2012)
  • Author(s): 小笠原正道
  • Journal Title: Journal of Organic Chemistry Volume: 77 Issue: 12 Pages: 5406-5410
  • DOI: 10.1021/jo300511e
  • Peer Reviewed
• [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
• [Presentation] alladium-Catalyzed Asymmetric Synthesis of Axially Chiral Allenes and Application to Synthesis of Allenic Natural Products (2013)
  • Author(s): Masamichi Ogasawara
  • Organizer: The 48th Advances in Organic, Bioorganic and Pharmaceutical Chemistry
  • Place of Presentation: Harmony Hotel (Spindleruv Mlyn, Czech Republic)
  • Invited
• [Presentation] Asymmetric Total Synthesis of Axially Chiral Naturally Occurring Allenes Utilizing Enantioselective Palladium-Catalyzed Reaction (2012)
  • Author(s): Masamichi Ogasawara, Mayuka Suzuki, Tamotsu Takahashi
  • Organizer: 59th Symposium on Organometallic Chemistry, Japan
  • Place of Presentation: 大阪大学(大阪府)