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2005 Fiscal Year Final Research Report Summary

Highly stereoselective and oxydative addition of protic molecules to iridium(I) complexes and asymmetric hydrogenation of prochiral imines.

Research Project

Project/Area Number 15550090
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

YAMAGATA Tsuneaki  Osaka University, Graduate School of Engineering Science, Division of Chemistry, Research Associate, 大学院・基礎工学研究科, 助手 (70166594)

Project Period (FY) 2003 – 2005
Keywordsasymmetric / hydrogenation / iridium / catalyst / carboxylato / imine / optical active / amine
Research Abstract

Mononuclear iridium(III) complexes of general formula IrX(H)(O_2CR)[(S)-binap](2, R=CH_3 ; 3,R=Ph ; 4,R=C_6H_4CH_3-p ; a, X=Cl ; b, X=Br ; c, X=I) were prepared by one-pot reaction of [Ir(μ-X)(cod)]_2 with 2 equiv of (S)-BINAP [=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl] and an excess of the corresponding carboxylic acid in toluene. The structure of (S)-2-4 bearing an (S)-BINAP was confirmed to be OC-6-23-A (Λ-conformation) by X-ray analysis of (S)-4a-c. In this reaction, the iridium(I) complex {Ir(μ-Cl)[(S)-binap]}_2 [(S)-5a] and pentacoordinated iridium(I) complexes IrX(cod)[(S)-binap] [(S)-7b, X=Br ; (S)-7c, X=I] were generated prior to the oxidative addition of carboxylic acid. Cationic dinuclear iridium(III) complexes of general formula [{Ir(H)[(S)-binap]}_2(μ-X)_3]X [(S)-8 : a, X=Cl ; b, X=Br ; c, X=I] were prepared, and their cationic bifacial octahedral dinuclear structure was characterized by spectral data and combustion analysis. The anionic portion of these complexes could … More be replaced by NaPF_6, leading to the corresponding PF_6 salts [{Ir(H)[(S)-binap]}_2(μ-X)_3]PF_6 [(S)-8 : d, X=Cl ; e, X=Br ; f, X=I]. Iodo-acetate complexes of p-TolBINAP (=2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl) [(S)-9c] and SYNPHOS [=2,2',3,3'-tetrahydro(5,5'-bi-1,4-benzodioxin)-6,6'-diyl]bis(diphenylphosphine)] [(S)-10c] were also prepared according to the method used for the BINAP complex (S)-2c and were characterized spectroscopically. Cationic dinuclear complexes of p-TolBINAP [(S)-11c] and SYNPHOS [(S)-12c] were also generated. Using these complexes, the effect of halide variation was studied by asymmetric hydrogenation of 2-phenylpyrrolidine (13) and 2-phenyl-4,5,6,7-tetrahydro-3H-azepine (15) along with 2-phenylquinoline (16), and the results indicated that iodide complexes were better catalyst precursors for catalytic activity than the corresponding chloride and bromide complexes, but were not superior in enantioselectivity. I have acquired three patents. The titles of patents are as follows, a : Method for preparation of optically active neutral rhodium-phosphine complexes as asymmetric synthesis catalysts. b : Preparation of iridium complexes as catalysts for the synthesis of optically active amines. c : Preparation of optically active phenylamines. Less

  • Research Products

    (15 results)

All 2006 2005 2004

All Journal Article (13 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Oxidative Addition of RCOH and HX to Chiral Diphosphine Complexes of Iridium(I): Convenient Synthesis of Mononuclear Halo-Carboxylate Iridium(III) Oxidative Addition of RCO_2 and HX to Chiral Diphosphine Complexes of Iridium(I) : Convenient Synthesis of Mononuclear Halo-Carboxylate Iridium(III) Complexes and Cationic Dinuclear Triply Halogen-Bridged Iridium(III) Complexes and Their Catalytic Performance in Asymmetric Hydrogenation of Cyclic Imines and 2-Phenylquinoline2006

    • Author(s)
      Yamagata, Tsuneaki
    • Journal Title

      Organometallics 25・10

      Pages: 2505-2513

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Hexapalladium cluster : Unique cluster construction reaction of cyclic Pd_3(CNC_6H_3Me_2-2,6)6 and linear [Pd_3(CNC_6H_3Me_2-,6)_8]^<2+>2006

    • Author(s)
      Ohashi, Masato
    • Journal Title

      Journal of Organometallic Chemistry 691・11

      Pages: 2457-2464

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Oxidative Addition of RCO_2H and HX to Chiral Diphosphine Complexes of Iridium(I) : Convenient Synthesis of Mononuclear Halo-Carboxylate Iridium(III) Complexes and Cationic Dinuclear Triply Halogen-Bridged Iridium(III) Complexes and Their Catalytic Performance in Asymmetric Hydrogenation of Cyclic Imines and 2-Phenylquinoline.2006

    • Author(s)
      Yamagata, Tsuneaki, Tadaoka, Hiroshi, Nagata, Mitsuhiro, Hirao, Tsukasa, Kataoka, Yasutaka, Ratovelomanana-Vidal, Virginie, Genet, Jean Pierre, Mashima, Kazushi
    • Journal Title

      Organometallics 25(10)

      Pages: 2505-2513

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Hexapalladium cluster : Unique cluster construction reaction of cyclic Pd_3(CNC_6H_3Me_2-2,6)6 and linear [Pd_3(CNC_6H_3Me_2-2,6)_8]^<2+>2006

    • Author(s)
      Ohashi, Masato, Yi, Jianjun, Shimizu, Daisuke, Yamagata, Tsuneaki, Ohshima, Takashi, Mashima, Kazushi
    • Journal Title

      Journal of Organometallic Chemistry 691(11)

      Pages: 2457-2464

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] 「研究成果報告書概要(和文)」より2005

    • Author(s)
      Yasumoto, Takahiro
    • Journal Title

      Organometallics 24・14

      Pages: 3375-3377

  • [Journal Article] Isoselective Living Polymerization of 1-Hexene Catalyzed by Half-Metallocene Dimethyl Complexes of Hafnium with Bidentate N-Substituted (Iminomethyl)pyrrolyl Ligands2005

    • Author(s)
      Yasumoto, Takahiro, Yamagata, Isuneaki, Mashima, Kazushi
    • Journal Title

      Organometallics 24(14)

      Pages: 3375-3377

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] An Infinite Zigzag Chain of Alternating Cl-Pd-Pd-Cl and Mo-Mo Units2004

    • Author(s)
      Yi, Jianjun
    • Journal Title

      Inorganic Chemistry 43・21

      Pages: 6596-6599

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Rhodium and iridium complexes bearing an alkyloxazoline-substituted indenyl ligand(Indox ligand) and their stereoselective construction of metal-centered chirality2004

    • Author(s)
      Kataoka, Yasutaka
    • Journal Title

      Inorganica Chimica Acta 357・10

      Pages: 2965-2979

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Intramolecular Benzylation of an Imino Group of Tridenlate 2,5-Bis(N-aryliminomethyl)-pyrrolyl Ligands Bound Zirconium and Hafnium Gives Amido-Pyrrolyl Complexes That Catalyze Ethylene Polymerizalion2004

    • Author(s)
      Trsurugi, Hayato
    • Journal Title

      Organometallics 23・11

      Pages: 2797-2805

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] An Infinite Zigzag Chain of Alternating Cl-Pd-Pd-Cl and Mo-Mo Units.2004

    • Author(s)
      Yi, Jianjun, Miyabayashi, Takayuki, Ohashi, Masato, Yamagata, Tsuneaki, Mashima, Kazushi
    • Journal Title

      Inorganic Chemistry 43(21)

      Pages: 6596-6599

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Rhodium and iridium complexes bearing an alkyloxazoline-substituted indenyl ligand (Indox ligand) and their stereoselective construction of metal-centered chirality2004

    • Author(s)
      Kataoka, Yasutaka, Shimada, Koichi, Goi, Takahiro, Yamagata, Tsuneaki, Mashima, Kazushi, Tani, Kazuhide
    • Journal Title

      Inorganica Chimica Acta 357(10)

      Pages: 2965-2979

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Intramolecular Benzylation of an Imino Group of Tridentate 2,5-Bis(N-aryliminomethyl)-pyrrolyl Ligands Bound to Zirconium and Hafnium Gives Amido-Pyrrolyl Complexes That Catalyze Ethylene Polymerization2004

    • Author(s)
      Tsurugi, Hayato, Matsuo, Yutaka, Yamagata, Tsuneaki, Mashima, Kazushi
    • Journal Title

      Organometallics 23(11)

      Pages: 2797-2805

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Construction of Metal-Centered Chirality : Diastereoselective Addition of the Meerwein Reagent (Me_3OBF_4) to Rhodium Carbonyl Complexes Having the Cp'-P Ligand2004

    • Author(s)
      Kataoka, Yasutaka, Nakagawa, Yousuke, Shibahara, Atsushi, Yamagata, Tsuneaki, Mashima, Kazushi, Tani, Kazuhide
    • Journal Title

      Organometallicsc 23(9)

      Pages: 2095-2099

    • Description
      「研究成果報告書概要(欧文)」より
  • [Patent(Industrial Property Rights)] イリジウム錯体2006

    • Inventor(s)
      Mashima K., Yamagata T.
    • Industrial Property Rights Holder
      Takasago Internastional
    • Industrial Property Number
      WO2006022020
    • Filing Date
      2006-08-27
    • Acquisition Date
      2006-03-02
    • Description
      「研究成果報告書概要(和文)」より
  • [Patent(Industrial Property Rights)] 中性ロジウム-ホスフィン錯体の製造法2004

    • Inventor(s)
      Mashima K., Yamagata T., Tadaoka, H., Sayo, N.
    • Industrial Property Rights Holder
      Takasago Perfumery
    • Industrial Property Number
      JP 2005281252
    • Filing Date
      2004-03-30
    • Acquisition Date
      2005-10-13
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2007-12-13  

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