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2001 Fiscal Year Final Research Report Summary

Development of Practical Catalytic Asymmetric Hydrogenatioh Using Methanol as a Hydrogen Source

Research Project

Project/Area Number 12355032
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

TANI Kazuhide  Osaka University, Graduate School of Engineering Science, Professor, 基礎工学研究科, 教授 (60029444)

Co-Investigator(Kenkyū-buntansha) YAMAGATA Tsuneaki  Osaka University, Research Associate, 基礎工学研究科, 助手 (70166594)
KATAOKA Yasutaka  Osaka University, Associate Professor, 基礎工学研究科, 助教授 (90221879)
MASHIMA Kazushi  Osaka University, Associate Professor, 基礎工学研究科, 助教授 (70159143)
SAYO Noboru  Takasago Perfumery Co. Ltd., The Central research, Senior Researcher, 総合研究所, 主任研究員
KUMOBAYASHI Hidenori  Takasago Perfumery Co. Ltd., Director of the Central Research, 総合研究所, 所長(研究職)
Project Period (FY) 2000 – 2001
KeywordsIndium / Methanol / Dihydrogen / asymmetric Hydrogenation / Rhodium / BINAP / Stereoselective / O-H Activation
Research Abstract

In this project, we studied O-H activation with late-transition metal complexes. We have found that [Ir(μn-Cl)(binap)]_2 (1) can easily activate methanol and the complex 1 and its oxidative addition complex of methanol act as efficient hydrogenation catalyst precursors of alkyne using methanol as a hydrogen source. Although these Complexes act as catalyst precursors for asymmetric hydrogenation of prochiral olefins also, their catalytic activity was not high enough and the enantio-selectivity for hydrogenation of dehydroamino acids remained as high as 50 %ee. Complex 1 can also activate various kinds of carboxylic acids very easily and (S)-1 gave quantitatively and stereoselectively, mononuclear hydrido(carboxylato) complexes (S)-OC-6-23-A-[Ir(Cl)(H)(h^2-0_2CR){(S)-binap}] (R=Me, Ar) (2), among five possible stereoisomers. Complexes 2 were found very efficient catalyst precursors for asymmetric hydrogenation of imine. Especially, for hydrogenation of cyclic imines, very high optical in … More duction over 99 %ee was realized. So-called a neutral rhodium-diphosphine catalyst, "RhCl(diphosphine)", has been prepared in situ and used in many kinds of catalysis, but its isolation is rare and the complex has not been well characterized. We have succeeded in isolation and full characterization including X-ray analysis of the rhodium analogue of complex 1, [Rh(μ-Cl){(S)-binap}]_2 (3). Complex 3 has a very similar structure to that of 1 but the properties of 3 were very much different from those of complex 1 ; Complex 1 is very sensitive against air as well as protic molecules but complex 3 was inert against these substances even at heating conditions. As complex 3 is considered to be effective for activation of dihydrogen, more detailed studies on Complex 3 will be needed. A comparative studies between complexes 1 and 3 would provide useful information about their applications. In addition, we contributed a review article about O-H activation to a book, "Catalytic Heterofunctionalization" edited by A. Togni and H. Grutzmacher and published by Wiley-VCH. Less

  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] 片岡靖隆: "Configurationary Stable Metal-centered Chirality : Stereospecific and Regioselective Rhodaacylation of Alkynes Controlled by the Third Generation of the [Cp'-P]H Ligand"Chemical Communications. 841-842 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "1-Aza-1,3-butadiene Complexes of Tantalum : Preparation and Alkylation of TaCl_2(η^5-C_5Me_5)(η^4-1-aza-1,3-butadiene)"Journal of Organomellic Chemistry. 593-594. 69-76 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 押木俊之: "Substituent Effect on Organotin Tp^* Compounds as the Tp^* Reagent for Preparation of Mono Tp^* Complexes of Group 4-6 Metals (Tp^*=Tris(3,5-dimethylpyrazol-1-yl)hydroborate)"Bullctin of the Chemical Socciety, Japan. 73. 1735-1748 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 真島和志: "Convenient Synthesis of Anionic Dinuclear Ruthenium(II) Complexes [NR_2H_2][{RuCl(diphosphine)}_2(μ-Cl)_3][diphosphine=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl,2,2'-bis(di(p-tolyl)phosphino)-1,1'-binaphthyl, and 1,2-bis(diphenyl-phosphino)benzene] : Crystal Structure of [NEt_2H_2][{RuCl(1,2-bis(diphenylphosphino)-benzene)}_2(μ-Cl)_3]"Journal of Organomellic Chemistry. 607. 51-56 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松尾 豊: "Synthesis and Characterization of Bis(iminopyrrolyl)zirconium Complexes"Chemistry Letters. 1114-1115 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 田中光洋: "Unique Axial Interaction of a Quadruply-Bonded Cr(II)〓Cr(II) with Two Pt(II) Atoms in the Linearly Aligned Pt-Cr-Cr-Pt Supported by Four 6-Diphenylphosphino-2-pyridonate Ligands"Bulletin of the Chemical Socciety, Japan. 73. 67-75 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "Acetonitrile Accelerated Selective C-H Bond Activation of the Cationic Ir(I) Complex Having the PN/CH3 Heterochelate Hybrid Ligand"Chemistry Letters. 300-301 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松尾 豊: "Half-Metallocene Tantalum Complexes Bearing Methyl Methacrylate(MMA) and 1,4-Diaza-1,3-diene Ligands as MMA polymerizalion Catalysts"Angewandte Chemie International Edition. 40. 960-962 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "Highly Diastereoselective Dihydride Formation by Activation of Methanol with IrCl{(S)-binap}(PPh_3)"Chemical Communications. 1630-1631 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 片岡靖隆: "Stereospecific CO Insertion into the Rhodium-Methyl s Bond in [(Cp'-P)Rh(CO)(Me)]BF_4 and Deinsertion from[(Cp'-P)Rh(COMe)I] : Experimental Evidence for Methyl Migration"Organometallics. 20. 2431-2433 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松尾 豊: "Selective Formation of Homoleptic and Heteroleptic 2,5-Bis(N-aryliminomethyl)pyrrolyl Yttrium Complexes and Their Performance as Initiators of e-Caprolactone Polymerization"Organometallics. 20. 3510-3518 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松尾 豊: "Intramolecular Coupling Reaction of 1-Aza-1,3-butadiene Ligand and Iminoacyl Ligand Giving Amido-imido Complexes of Tantalum"Organometallics. 21. 138-143 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 松尾 豊: "Half-metallocene 1-Aza-1,3-butadiene Complexes of Tantalum : Auxiliary Ligand Effects on Controlling Coordnation Modes of 1-Aza-1,3-butadiene Ligand"Bull. Chem. Soc. Jpn.. 75(in press). (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 谷一英: "Catalytic Heterofunctionalization(O-H Activation and Addition to Unsaturated Systems)"Wiley-VCH ; Edited by A. Togni and H Grutzmacher. 46 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y. Kataoka, Y. Iwato, A. Shibahara, T. Yamagata, and K. Tani: "Configurationally Stable Metal-centered Chirality : Stereospecific and Regioselective Rhodaacylation of Alkynes Controlled by the Third Generation of the [Cp'-P]H Ligand"Chem. Commun.. 841-842 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Mashima, Y. Matsuo, and K. Tani: "1-Aza-1, 3-butadiene Complexes of Tantalum : Preparation and Alkylatipn of TaCl_2(η^5-C_5Me_5)(η^4-1-aza-l ,3-butadiene)"J. Organomet. Chem.. 593-594. 69-76 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Oshiki, K. Mashima, S-i. Kawamura, K. Tani, and K. Kitaura: "Substituent Effect on Organotin Tp* Compounds as the Tp* Reagent for the Preparation of Mono Tp* Complexes of Group 4-6 Metals (Tp* = Tris(3,5-dimethylpyrazol-1-yl)hydroborate)"Bull. Chem. Soc. Jpn.. 73. 1735-1748 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Mashima, T. Nakamura, Y, Matsuo, and K.Tani: "Convenient Synthesis of Anionic Dinuclear Ruthenium(II) Complexes [NR_2H_2] [{RuCl (diphosphine)}_2(μ-Cl)_3] [diphosphine = 2, 2'-bis(diphenylphosphino)-1, 1'-binaphthyl, 2, 2'bis(di(p-tolyl)phosphino)-1, 1'-binaphthyl, and 1 ,2-bis(diphenylphosphino)benzene] : Crystal Structure of [NEt_2H_2][{RuCl(1 ,2-bis(diphenylphosphino)benzene)}_2(μ-Cl)_3]"J. Organmet. Chem.. 607. 51-56 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Matsuo, K. Mashima, and K. Tani: "Systhesis and Characterization of Bis(iminopyrroly)zirconium Complexes"Chem. Lett.. 1114-1115 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Tanaka, K. Mashima, M. Nishino, S. Takeda, W. Mori, K. Tani, K. Yamaguchi, and A. Nakamura: "Unique Axial Interaction of a Quadruply-Bonded Cr(II)〓Cr(II) with Two Pt(II) Atoms in the Linearly Aligned Pt-Cr-Cr-Pt Supported by Four 6-Diphenylphosphino-2-phridonate Ligands"Bull. Chem. Soc. Jpn.. 73. 67-75 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Matsuo, K. Mashima, and K. Tani: "Half-Metallocene Tantalum Complexes Bearing Methyl Methacrylate(MMA) and 1, 4-Diaza-1, 3-diene Ligands as MMA Polymerization Catalysts"Angew. Chem. Int. Ed.. 40. 960-962 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Kataoka, K Shizuma, T. Yamagata, and K. Tani: "Acetonitrile Accelerted Stereoselective C-H Bond Activation of the Cationic Ir(I) Complex Having the PN/CH3 Heterochelate Hybrid Ligand"Chem. Lett.. 300-301 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K Kataoka, A. Shibahara, T. Yamagata, and K. Tani: "Stereospecific CO Insertion into the Rh-Methyl s-Bond in [(Cp'-P)Rh(CO)(Me)]BF_4 and Deinsertion from [(Cp'-P)Rh(COMe)I] : Experimental Evidences for Methyl Migration"Organometallics. 20. 2431-2433 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Tani, K. Nakajima, A. Iseki, and T. Yamagata: "Highly Diatereoselective Dihydride Formation by Activation of Methanol with IrCl{(S)-binap}(PPh)_3)"Chem. Commun.. 1630-1631 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Matsuo, K. Mashima, and K. Tani: "Selective Formation of Homoleptic and Heteroleptic 2, 5-Bis(N-aryliminomethyl)pyrrolyl Yttrium Complexes and Their Performance as Initiators of e-Caprolactone Polymerization"Organometallics. 20. 3510-3518 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Matsuo, K. Mashima, and K. Tani: "Intramolecular Coupling Reaction of 1-Aza-1, 3-butadiene Ligand and Iminoacyl Ligand Giving Amido - imido Complexes of Tantalum"Organometallics. 21. 138-143 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Matsuo, K. Mashima, and K. Tani: "Half-metallocene l-Aza-1,3-butadiene Complexes of Tantalum : Auxiliary Ligand Effects on Controlling Coordination Modes of 1-Aza-1, 3-butadiene Ligand"Bull. Chem. Soc. Jpn.. (in press). (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Tani and Y. Kataoka: "O-H Activation and Addition to Unsaturated Systems"Catalytic Heterofunctionnalization", Wiley-VCH, Ed. by A. Togni and H. Grutzmacher. 171-216 (2001)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2003-09-17  

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