Studies on the Transition Metal-Rare Earth Metal/Dinuclear Schiff Base Catalysts, Mechanistic Studies and Application to New Asymmetric Reactions

• Project/Area Number: 20685008
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: MATSUNAGA Shigeki 東京大学, 大学院・薬学系研究科, 准教授 (50334339)
• Project Period (FY): 2008 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥25,610,000 (Direct Cost: ¥19,700,000、Indirect Cost: ¥5,910,000); Fiscal Year 2010: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000); Fiscal Year 2009: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000); Fiscal Year 2008: ¥10,010,000 (Direct Cost: ¥7,700,000、Indirect Cost: ¥2,310,000)
• Keywords: 触媒 / 不斉合成 / 不斉触媒 / サレン / 非天然アミノ酸 / 医薬品合成 / 希土類触媒 / シッフ塩基 / 複核錯体

Research Abstract

Characterization of hetero-dinuclear rare earth metal/transition metal Schiff base complexes, as well as their applications to various enantioselective reactions have been investigated. Catalytic asymmetric nitro-Mannich-type reactions, catalytic asymmetric α-addition of isocyanato esters to aldehydes, and so on have been successfully developed, leading to providing useful synthetic methods for chiral nitrogen-containing building blocks. Thus, the achievement can contribute for the efficient synthesis of pharmaceuticals.

Research Products

• [Journal Article] Heterobimetallic Transition Metal/Rare Earth Metal Bifunctional Catalysis: a Cu-SnrSchiff Base Complex for syn-Selective Catalytic Asymmetric Nitro-Mannich Reaction (2010)
  • Author(s): S. Handa, V. Gnanadesikan, S. Matsunaga, M Shibasaki
  • Journal Title: J. Am Chem Soc Volume: 132(13) Issue: 13 Pages: 4925-4934
  • DOI: 10.1021/ja100514y
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asynmetric Vinylogous Mannich -type and Michael Reactions of an α, β-Unsaturated y Butyrolactam Under Dinuclear Nickel Catalysis (2010)
  • Author(s): N. E. Shepherd, FL Tanabe, Y. Xu, S. Matsunaga, M. Sibasaki
  • Journal Title: J. Am Chem Soc Volume: 132(11) Issue: 11 Pages: 3666-3667
  • DOI: 10.1021/ja1002636
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Synthesis of 3-Aminooxindoles: Enantiofacial Selectivity Switch in Bimetallic vs Monometallic Schiff Base Catalysis (2010)
  • Author(s): S. Mouri, Z. Chen, H. Mitsunuma, M. Furutachi, S. Matsunaga and M. Shibasaki
  • Journal Title: J. Am. Chem. Soc. Volume: 132 Issue: 4 Pages: 1255-1257
  • DOI: 10.1021/ja908906n
  • Peer Reviewed
• [Journal Article] Heterobimetallic Transition Metal/Rare Earth Metal Bifunctional Catalysis : A Cu/Sm/Schiff Base Complex for Syn-Selective Catalytic Asymmetric Nitro-Mannich Reaction (2010)
  • Author(s): Handa, S; Gnanadesikan, V.; Matsunaga, S.; Shibasaki, M.
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 4925-4934
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Vinylogous Mannich-Type and Michael Reactions of an α,β-Unsaturated γ-Butyrolactam under Dinuclear Nickel Catalysis (2010)
  • Author(s): Shepherd, N.E.; Tanabe, H.; Xu, Y.; Matsunaga, S.; Shibasaki, M.
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 3666-3667
  • Peer Reviewed
• [Journal Article] A Heterobimetallic Ni/La-salan Complex for Catalytic Asymmetric Decarboxylative 1,4-Addition of Malonic Acid Half-Thioester (2010)
  • Author(s): Furutachi, M.; Mouri, S.; Matsunaga, S.; Shibasaki, M.
  • Journal Title: Chem.Asian.J. Volume: 5 Pages: 2351-2354
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Synthesis of 3-Aminooxindoles : Enantiofacial Selectivity Switch in Bimetallic vs Monometallic Schiff Base Catalysis (2010)
  • Author(s): S.Mouri, Z.Chen, H.Mitsunuma, M.Furutachi, S.Matsunaga, M.Shibasaki
  • Journal Title: J.Am.Chem.Soc. 132 Pages: 1255-1257
  • Peer Reviewed
• [Journal Article] Construction of Contiguous Tetrasubstituted Chiral Carbon Stereocenters via Direct Catalytic Asymmetric Aldol Reaction of α-Isothiocyanato Esters to Ketones (2009)
  • Author(s): T. Yoshino, H. Morimoto, G. Lu, S. Matsunaga and M. Shibasaki
  • Journal Title: J. Am. Chem. Soc. Volume: 131 Issue: 47 Pages: 17082-17083
  • DOI: 10.1021/ja908571w
  • Peer Reviewed
• [Journal Article] A Heterobimetallic Ga/Yb-Schiff Base Complex for Catalytic Asymmetric a-Addition of Isocyanides to Aldehydes (2009)
  • Author(s): H. Mihara, Y. Xu, N. E. Shepherd, S. Matsunaga, and M. Shibasaki
  • Journal Title: J. Am Chem Soc Volume: 131(24) Issue: 24 Pages: 8384-8385
  • DOI: 10.1021/ja903158x
  • Peer Reviewed
• [Journal Article] A Homodinuclear Mn(III)_2-Schiff Base Complex for Catalytic Asymmetric 1,4-Additions of Oxindoles to Nitroalkenes (2009)
  • Author(s): Y. Kato, M. Furutachi, Z. Chen, H. Mistunuma, S. Matsunaga and M. Shibasaki
  • Journal Title: J. Am. Chem. Soc. Volume: 131 Issue: 26 Pages: 9168-9169
  • DOI: 10.1021/ja903566u
  • Peer Reviewed
• [Journal Article] A Stable Homodinuclear Biscobalt(III)-Schiff Base Complex for Catalytic Asymmetric 1,4-Additions of β-Keto Esters to Alkynones (2009)
  • Author(s): Z. Chen, M. Furutachi, Y. Kato, S. Matsunaga and M. Shibasaki
  • Journal Title: Angew. Chem. Int. Ed. Volume: 48 Issue: 12 Pages: 2218-2220
  • DOI: 10.1002/anie.200805967
  • Peer Reviewed
• [Journal Article] A Heterobimetallic Ga/Yb-Schiff Base Complex for Catalytic Asymmetric α-Addition of Isocyanides to Aldehydes (2009)
  • Author(s): H.Mihara, Y.Xu, N.E.Shepherd, S.Matsunaga, M.Shibasaki
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 8384-8385
  • Peer Reviewed
• [Journal Article] A Homodinuclear Mn(III)_2-Schiff Base Complex for Catalytic Asymmetric 1, 4-Additions of Oxindoles to Nitroalkenes (2009)
  • Author(s): Y.Kato, M.Furutachi, Z.Chen, H.Mitsunuma, S.Matsunaga, M.Shibasaki
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 9168-9169
  • Peer Reviewed
• [Journal Article] A Stable Homodinuclear Biscobalt(III)Schiff Base Complex for Catalytic Asymmetric 1,4-Additions of β-Keto Esters to Alkynones (2009)
  • Author(s): Z. Chen, F. Makoto, Y. Kato, S. Matsunaga, M. Shibasaki
  • Journal Title: Angew. Chem. Mt. Ed 48 Pages: 2218-2220
  • Peer Reviewed
• [Journal Article] Direct antiSelective Catalytic Asymmetric Mannich-type Reactions of aKetoanilides for y-Amino Amides and Azetidine-2-amides Synthesis (2009)
  • Author(s): Y. Xu, G. Lu, S. Matsunaga, M. Shibasaki
  • Journal Title: Angew. Chem. In t. Ed 48(印刷中)
  • Peer Reviewed
• [Journal Article] Direct Catalytic Asymmetric Mannich-type Reaction of R-Keto Phosphonate Using a Dinuclear Ni_2-Schiff Base Complex (2008)
  • Author(s): Z. Chen, K. Yakura, S. Matsunaga, M. Shibasaki
  • Journal Title: Org. Lett 10 Pages: 3239-3242
  • Peer Reviewed
• [Presentation] Development of multimetallic asymmetric catalysisthrough chiral ligand design (2009)
  • Author(s): S. Matsunaga
  • Organizer: 第4回三井化学触媒科学国際シンポジウム
  • Place of Presentation: カズサアカデミアホール(木更津)(受賞講演)
  • Year and Date: 2009-03-11
• [Presentation] Development of multimetallic asymmetric catalysis through chiral ligand design (2009)
  • Author(s): S. Matsunaga
  • Organizer: 第4回三井化学触媒科学国際シンポジウム
  • Place of Presentation: カズサアカデミアホール(木更津)
  • Year and Date: 2009-03-11
• [Presentation] 不斉配位子の設計に基づく多中心協奏機能不斉触媒の開発 (2009)
  • Author(s): 松永茂樹
  • Organizer: 第8回化学・材料研究セミナー
  • Place of Presentation: 九州大学理学部(箱崎キャンパス)
  • Year and Date: 2009-01-24
• [Presentation] Bimetallic Cooperative Asymmetric Catalysis for C-C Bond Formation; Green Chemistry For Catalytic C-C Bond Formation (2008)
  • Author(s): S. Matsunaga
  • Organizer: USA -Japan Young Chemist Exchange
  • Place of Presentation: University of Texas, Austin, USA(招待講演)
  • Year and Date: 2008-07-11
• [Remarks]
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  • URL: http://www.f.u-tokyo.ac.jp/~kanai/index.html
• [Remarks]
  • URL: http://www.f.u-tokyo.ac.jp/~kanai/index.html
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  • URL: http://www.f.u-tokyo.ac.jp/~kanai/index.html
• [Patent(Industrial Property Rights)] 光学活性ジマンガン錯体 (2009)
  • Inventor(s): 柴崎正勝、松永茂樹、加藤祐子、陳志華、古舘信
  • Industrial Property Rights Holder: 日産化学工業株式会社
  • Industrial Property Number: 2009-047245
  • Filing Date: 2009-02-27