Development of novel chiral ligands based on dienic helical chiralityand their application in asymmetric synthesis

2008 Fiscal Year Final Research Report

• Project/Area Number: 19550099
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: OGASAWARA Masamichi Hokkaido University, 触媒化学研究センター, 准教授 (70301231)
• Project Period (FY): 2007 – 2008
• Keywords: 螺旋不斉 / ホスフィン / ジエン / 不斉配位子 / 不斉合成

Research Abstract

本研究では、立体配座の自由度を規制した共役ジエン構造に基づく螺旋不斉を基とする新規ジホスフィン配位子を設計し、その合成を行った。得られたラセミ体の化合物は、キラルHPLCにより熱的に安定な2つのエナンチオマーに分割することがでた。さらには、ジホスフィンオキシドを2つのエナンチオマーに効率良く分割する手法を見出した。一方、ジホスフィンオキシドのシランによる還元では炭素ーリン結合の開裂がおこり、目的とするホスフィンを得る事はできなかった。光学活性ジホスフィンオキシドを、不斉有機触媒としてアリルシランによる不斉アリル化に応用し、優れた不斉誘起能があることを見出した。

Research Products

• [Journal Article] Transition-Metal-Catalyzed EnantioselectiveSynthesis of Compounds with Non-Centrochirality (2009)
  • Author(s): Ogasawara, M.; Watanabe, S.
  • Journal Title: Synthesis (in press)
  • Peer Reviewed
• [Journal Article] Catalytic EnantioselectiveSynthesis of Axially Chiral Allenes (2009)
  • Author(s): Ogasawara, M
  • Journal Title: Tetrahedron : Asymmetry 20 Pages: 259-271
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Synthesisof Endocyclic Allenes and Their Applicationin Stereoselective [2+2] Cycloaddition with Ketenes (2009)
  • Author(s): Ogasawara, M.; Okada, A.; Nakajima, K.; Takahashi, T.
  • Journal Title: Org. Lett 11 Pages: 177-180
  • Peer Reviewed
• [Journal Article] Preparation of [4]- and [5] Ferrocenophanes by Ruthenium-Catalyzed Ring-Closing Ene-Yne Metathesis (2008)
  • Author(s): Ogasawara, M.; Watanabe, S.; Nakajima, K.; Takahashi, T.
  • Journal Title: Organometallics 27 Pages: 6565-6569
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of Planar-Chiral Ferrocenes by Mo- orRu-Catalyzed Enantioselective Metathesis (2008)
  • Author(s): Ogasawara, M.; Watanabe, S.; Nakajima, K.; Takahashi, T.
  • Journal Title: Pure Appl. Chem. 80 Pages: 1109-1113
  • Peer Reviewed
• [Journal Article] 「パラジウム錯体触媒による置換アレン類の立体選択的合成法の開発とその応用」 (2008)
  • Author(s): 小笠原正道
  • Journal Title: 有機合成化学協会誌 66 Pages: 100-109
  • Peer Reviewed
• [Journal Article] Unprecedented Formation of μ-Vinylidene Complexes from Phospharuthenocene and Acyl Chloride via Activation of the C=ODouble Bond (2007)
  • Author(s): Ogasawara, M.; Sakamoto, T.; Ito, A.; Ge, Y.; Nakajima, K.; Takahashi, T.; Hayashi, T.
  • Journal Title: Organometallics 26 Pages: 6698-6700
  • Peer Reviewed
• [Journal Article] Alkenylzirconocene-Mediated Preparation of Alkenylphosphines (2007)
  • Author(s): Miyaji, T.; Xi, Z.; Ogasawara, M.; Nakajima, K.; Takahashi, T
  • Journal Title: J. Org. Chem 72 Pages: 8737-8740
  • Peer Reviewed
• [Journal Article] Synthesis, Structure, and Reactivity of(1,2,3-η^3-Butadien-3-yl) palladium Complexes (2007)
  • Author(s): Ogasawara, M.; Okada, A.; Watanabe, S.; Fan, L.; Uetake, K.; Nakajima, K.; Takahashi, T.
  • Journal Title: Organometallics 26 Pages: 5025-5029
  • Peer Reviewed
• [Journal Article] Preparation and Characterization of 1,1'-Diphosphaferrocenes with Linearly Fused Six-Membered Carbocycles J (2007)
  • Author(s): Ogasawara, M.; Sakamoto, T.; Nakajima, K.; Takahashi, T.
  • Journal Title: Organomet. Chem 692 Pages: 55-59
  • Peer Reviewed
• [Presentation] Transition-Metal-Catalyzed Enantioselective Synthesis of Planar-ChiralTransition-Metal Complexes (2009)
  • Author(s): 小笠原正道
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学船橋キャンパス(船橋市)
  • Year and Date: 20090327-30
• [Presentation] 遷移金属触媒による非中心不斉の立体制御-軸不斉アレンと面不斉メタロセンの触媒的不斉合成 (2009)
  • Author(s): 小笠原正道
  • Organizer: 北海道大学グローバルCOE シンポジウム
  • Place of Presentation: 北海道大学(札幌市)
  • Year and Date: 2009-10-24
• [Presentation] 面不斉メタロセンの触媒的不斉合成と光学活性メタロセン・ポリマー合成への応用 (2008)
  • Author(s): 小笠原正道
  • Organizer: 京都大学グローバルCOE有機若手ワークショップ
  • Place of Presentation: 京都大学(京都市)
  • Year and Date: 20080911-12
• [Presentation] Ring-Opening Metathesis Polymerization of Planar-Chiral Butadiene-Bridged Ferrocenophanes (2008)
  • Author(s): Ogasawara, M.; Sakamoto, T.; Nakajima, K.; Takahashi, T.
  • Organizer: 23^<rd> International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes (France)
  • Year and Date: 20080713-18
• [Presentation] Enantioselective Synthesis of Planar-Chiral Metallocenes by Mo- or Metathesis (2008)
  • Author(s): Ogasawara, M.; Watanabe, S.; Nakajima, K.; Takahashi, T.
  • Organizer: 23^<rd> International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes (France)
  • Year and Date: 20080713-18
• [Presentation] Enantioselective Synthesisof Planar-Chiral Ferrocenes by AsymmetricRing-Closing Metathesis (2008)
  • Author(s): Ogasawara, M.; Watanabe, S.; Nakajima, K.; Takahashi, T.
  • Organizer: 235^<th> ACS National Meeting
  • Place of Presentation: New Orleans (USA)
  • Year and Date: 20080406-10
• [Presentation] Palladium-CatalyzedAsymmetric Synthesis of Axially ChiralAllenylsilanes and Their Application in Chirality Transfer Reactions (2008)
  • Author(s): Ogasawara, M.; Okada, A.; Sorgel, S.; Takahashi, T.
  • Organizer: 235^<th> ACS National Meeting
  • Place of Presentation: New Orleans(USA)
  • Year and Date: 20080406-10
• [Presentation] Transition-Metal-Catalyzed Asymmetric Synthesis of Planar-Chiral Metallocenes (2008)
  • Author(s): Ogasawara, M
  • Organizer: Taiwan-Japan International Symposium on Organic Chemistry Molecular Science
  • Place of Presentation: NationalTaipei University of Technology (Taipei)
  • Year and Date: 20080118-20
• [Presentation] Pd-Catalyzed Asymmetric Synthesis of Axially Chiral Allenes and Their Application in Organic Transformations (2008)
  • Author(s): Ogasawara, M
  • Organizer: 1st Japan-Singapore Bilateral Symposium onCatalysis
  • Place of Presentation: National University ofSingapore (Singapore)
  • Year and Date: 20080107-08
• [Presentation] 均一系触媒による遷移金属錯体の立体選択的分子変換~面不斉メタロセンの触媒的不斉合成の開発 (2008)
  • Author(s): 小笠原正道
  • Organizer: 有機化学と無機化学の交流シンポジウム
  • Place of Presentation: 岡山大学(岡山市)
  • Year and Date: 2008-07-29
• [Presentation] Catalytic Asymmetric Synthesis of Planar-Chiral Ferrocene Derivatives and Their Application to Optically Active Polymers (2008)
  • Author(s): Ogasawara, M
  • Organizer: China-Japan Joint Symposium on Functional Materials toward Future Catalysts
  • Place of Presentation: Chinese Academy of Sciences (Beijing)
  • Year and Date: 2008-01-16
• [Presentation] Pd-Catalyzed AsymmetricSynthesis of Axially Chiral Allenes and TheirApplication in Organic Transformations (2007)
  • Author(s): Ogasawara, M
  • Organizer: 7th Tateshina Conference on Organic Chemistry
  • Place of Presentation: Tateshina (Nagano)
  • Year and Date: 20071109-11
• [Presentation] 面不斉メタロセンの触媒的不斉合成と光学活性メタロセンポリマーへの応用 (2007)
  • Author(s): 小笠原正道
  • Organizer: 第37 回石油・石油化学討論会
  • Place of Presentation: 札幌コンベンションホール(札幌市)
  • Year and Date: 20071025-27
• [Presentation] 遷移金属錯体触媒による置換アレン類の立体選択的合成法の開発とその応用 (2007)
  • Author(s): 小笠原正道
  • Organizer: 第24回有機合成化学セミナー
  • Place of Presentation: 淡路夢舞台(淡路市)
  • Year and Date: 20070912-14
• [Presentation] Mo-Catalyzed AsymmetricMetathesis Routes to Planar-Chiral FerroceneDerivatives (2007)
  • Author(s): Ogasawara, M.; Watanabe, S.; Nakajima, K.; Takahashi, T.
  • Organizer: 14th IUPAC Symposium onOrganometallic Chemistry Directed Towards Organic Synthesis (OMCOS-14)
  • Place of Presentation: Nara Centennial Hall (Nara)
  • Year and Date: 20070802-06
• [Presentation] Preparation of Bridged-Ferrocenes by Ruthenium-Catalyzed Ene-Yne Metathesis (2007)
  • Author(s): Ogasawara, M.; Watanabe, S.; Nakajima, K.; Takahashi, T.
  • Organizer: 14th IUPAC Symposium on Organometallic ChemistryDirected Towards Organic Synthesis (OMCOS-14)
  • Place of Presentation: Nara CentennialHall (Nara)
  • Year and Date: 20070802-06
• [Presentation] Palladium-Catalyzed Synthesis of Cyclic Allenes: Scope and Limitation (2007)
  • Author(s): Ogasawara, M.; Okada, A.; Nakajima, K.; Takahashi, T.
  • Organizer: 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-14)
  • Place of Presentation: Nara Centennial Hall (Nara)
  • Year and Date: 20070802-06
• [Presentation] Preparation of Planar-ChiralBridged-Ferrocenes and Their Application toRing-Opening Metathesis Polymerization (2007)
  • Author(s): Ogasawara, M.; Sakamoto, T.; Nakajima, K.; Takahashi, T.
  • Organizer: 14th IUPAC Symposium on OrganometallicChemistry Directed Towards Organic Synthesis (OMCOS-14)
  • Place of Presentation: NaraCentennial Hall (Nara)
  • Year and Date: 20070802-06
• [Book] Product Class 1 : CumulenesIn Science of Synthesis, Houben-Weyl,Methods of Molecular Transformations : Vol.44 (Compounds with All-Carbon Functions : Cumulenes and Allenes) (2008)
  • Author(s): Ogasawara, M
  • Total Pages: 9-70
  • Publisher: Krause, N., ed., Georg Thieme Verlag : Stuttgart