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Novel Ruthenium-Catalyzed Synthesis of Polycarboxylic Acid Derivatives

Research Project

Project/Area Number 13555246
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 有機工業化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

MITSUDO Take-aki  Kyoto Univ., Graduate School of Eng., Professor, 工学研究科, 教授 (90026344)

Co-Investigator(Kenkyū-buntansha) URA Yasuyuki  Kyoto Univ., Graduate School of Eng., Instructor, 工学研究科, 助手 (40335196)
WADA Kenji  Kyoto Univ., Graduate School of Eng., Lecturer, 工学研究科, 講師 (10243049)
KONDO Teruyuki  Kyoto Univ., Graduate School of Eng., Associate Professor, 工学研究科, 助教授 (20211914)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥13,600,000 (Direct Cost: ¥13,600,000)
Fiscal Year 2003: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2002: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2001: ¥8,800,000 (Direct Cost: ¥8,800,000)
KeywordsRuthenium catalyst / Allylic alcohols / Alkyne / Benzannulation / o-Phthalic acid / Acrylates / Origomerization / Norbornene / メタラサイクル / [2+2+2]付加環化反応 / o-フタル酸エステル / 二量化反応 / 2-ノルボルネン / カルボニル化反応 / 付加環化反応 / 炭素-炭素結合切断 / シクロプロペノン / )アリルアルコール / ピラノピランジオン / ベンゼンポリカルボン酸 / ピロノピロン
Research Abstract

Both aliphatic and aromatic polycarboxylic acid derivatives are highly important intermediates in chemical industry. In this study, we developed the following novel ruthenium-catalyzed syntheses of polycarboxilic acid derivatives involving cross-coupling and cycloaddition reactions. First, pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru_3(CO)_<12> and NEt_3 in THF under 15 atm of carbon monoxide at 140℃ for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions. All pyranopyrandiones prepared in this study are new compounds, which are quite attractive as novel functional monomers due to their … More characteristic physical and chemical properties. Then, a catalyst system consisting, of Cp*RuCl(cod)/PPh_3 [Cp* = pentamethylcyclopentadienyl, cod 1,5-cyclooctadiene] for the novel cross-benzannulation of 2 equip of dialkyl acetylenedicarboxylate with an allylic compound has been developed. As an example, the reaction of dimethyl acetylenedicarboxylate with allyl alcohol in the presence of 4 mol % Cp*RuCl(cod) and PPh_3 under reflux in toluene for 5 h gave tetramethyl 5-methyl-1,2,3,4-benzenetetracarboxylate in an isolated yield of 84%. Furthermore, a highly chemoselective intermolecular [2 + 2 + 2] cycloaddition of 2 eqiv of terminal alkynes with dimethyl acetylenedicarboxylate, which enables the straightforward synthesis of dialkylated o-phthalates, was successfully accomplished using a ruthenium catalyst, Cp*RuCl(cod). The co-cyclotrimerization of alkynes and acetylenedicarboxylates usually affords 1:2 adducts (1,2,3,4-benzenetetracarboxylates), however, in the present reaction 2:1 adducts (o-phthalates) are the major products unprecedentedly. Recently, we have also reported the novel zerovalent ruthenium complex Ru(η^6-cot)(dmfm)_2, which showed high catalytic activity in a unique dimerization of 2,5-norbornadiene to novel half-cage compounds, PCTD [pentacyclo[6.6.0.0^<2,6>.0^<3,13>.0^<10,14>]tetradeca-4,11-diene]. During our further investigation of the reactivity of this complex, we found that the reaction with p-quinones gave Ru(η^6-cot)(p-quinone) complexes, while the reaction with arenes gave novel (η^6-arene)Ru(dmfm)_2 complex. All reactionsproceeded via the direct ligand exchange reactions of cot and/or dmfm in Ru(η^6-cot)(dmfm)_2, and the new complexes prepa-red here can be expected as efficient catalysts for the synthesis of aliphatic and aromatic polycarboxylic acid derivatives. Less

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] Take-aki Mitsudo: "Ruthenium Complex-Catalyzed Formation and Cleavage of Carbon-Carbon o-Bonds. On the Requirement of Highly Qualified Tuning of the Reaction Conditions"Synlett. 3号. 309-321 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Teruyuki Kondo: "Rapid Ruthenium-Catalyzed Synthesis of Pyranopyrandions by Reconstructive Carbonylation of Cyclopropenones Involving C-C Bond Cleavage"Journal of the American Chemical Society. 124・24. 6824-6825 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Teruyuki Kondo: "Novel Sysnthesis of Benzenepolycarboxylates by Ruthenium-Catalyzed Cross-Benzannulation of Acetylenedicarboxylates with Allylic Compounds"Organometallics. 21・21. 4564-4567 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yasuyuki Ura: "Synthesis and Structures of Novel Zerovalent Ruthenium p-Quinone Complexes and Bimetallic p-Biquinone Complex"Organometallics. 22・1. 77-82 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yasuyuki Ura: "Synthesis of Novel Zerovalent Ruthenium η^6-Arene Complexes via Direct Displacement of a 1,3,5-Cyclooctatriene Ligand by Arenes"Organometallics. 22・9. 1863-1867 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yasuyuki Ura: "Ruthenium-Catalyzed Synthesis of o-Phthalates by Highly Chemoselective Intermolecular [2+2+2] Cycloaddition of Terminal Alkynes and Dimethyl Acetylenedicarboxylate"Journal of Molecular Catalysis A : Chemical. 209・1-2. 35-39 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Take-aki Mitsudo, Teruyuki Kondo: "Ruthenium Complex-Catalyzed Formation and Cleavage of Carbon-Carbon σ-Bonds. On the Requirement of Highly Qualified Tuning of the Reaction Conditions"Synlett. No.3. 309-321 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Teruyuki Kondo, Yushi Kaneko, Yoshinori Taguchi, Ayako Nakamura, Takumi Okada, Masashi Shiotsuki, Yasuyuki Ura, Kenji Wada, Take-aki Mitsudo: "Rapid Ruthenium-Catalyzed Synthesis of Pyranopyrandions by Reconstructive Carbonylation of Cyclopropenones Involving C-C Bond Cleavage"Journal of the American Chemical Society. Vol.124, No.24. 6824-6825 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Teruyuki Kondo, Yushi Kaneko, Fumiaki Tsunawaki, Takumi Okada, Masashi Shiotsuki, Yasuhiro Morisaki, Take-aki Mitsudo: "Novel Synthesis of Benzenepolycarboxylates by Ruthenium-Catalyzed Cross-Benzannulation of Acetylenedicarboxylates with Allylic Compounds"Organometallics. Vol.21, No.21. 4564-4567 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yasuyuki Ura, Yoshitaka Sato, Masashi Shiotsuki, Toshiaki Suzuki, Kenji Wada, TeruyukiKondo, Take-aki Mitsudo: "Synthesis and Structures of Novel Zerovalent Ruthenium p-Quinone Complexes and a Bimetallic p-Biquinone Complex"Organometallics. Vol.22, No.1. 77-82 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yasuyuki Ura, Masashi Shiotsuki, Kazuo Sadaoka, Toshiaki Suzuki, Teruyuki Kondo, Take-aki Mitsudo: "Synthesis of Novel Zerovalent Ruthenium η^6-Arene Complexes via Direct Displacement of a 1,3,5-Cyclooctatriene Ligand by Arenes"Organometallics. Vol.22, No.9. 1863-1867 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yasuyuki Ura, Yoshitaka Sato, Masashi Shiotsuki, TeruyukiKondo, Take-aki Mitsudo: "Ruthenium-Catalyzed Synthesis of o-Phthalates by Highly Chemoselective Intermolecular [2 + 2 + 2] Cycloaddition of Terminal Alkynes and Dimethyl Acetylenedicarboxylate"J.Mol.Catal.A : Chemical. Vol.209, No.1-2. 35-39 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Masashi Shiotsuki: "Synthesis and Structure of Novel Zerovalent Ruthenium Complexes with Three Pyridine Ligands or Tridentate Pyridyl Ligands"Organometallics. 22・6. 1332-1339 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yasuyuki Ura: "Synthesis of Novel Zerovalent Ruthenium η^<6->Arene Complexes via Direct Displacement of a 1,3,5-Cyclooctatriene Ligand by Arenes"Organometallics. 22・9. 1863-1867 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yasuyuki Ura: "Ruthenium-Catalyzed Synthesis of o-Phthalates by Highly Chemoselective Intermolecular [2+2+2] Cycloaddition of Terminal Alkynes and Dimethyl Acetylenedicarboxylate"Journal of Molecular Catalysis A : Chemical. 209・1-2. 35-39 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Teruyuki Kondo: "Rapid Ruthenium-Catalyzed Synthesis of Pyranopyrandions by Reconstructive Carbonylation of Cyclopropenones Involving C-C Bond Cleavage"Journal of the American Chemical Society. 124・24. 6824-6825 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Teruyuki Kondo: "Novel Synthesis of Benzenepolycarboxylates by Ruthenium-Catalyzed Cross-Benzannulation of Acetylenedicarboxylates with Allylic Compounds"Organometallics. 21・21. 4564-4567 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yasuyuki Ura: "Synthesis and Structures of Novel Zerovalent Ruthenium p-Quinone Complexes and Bimetallic p-Biquinone Complex"Organometallics. 22・1. 77-82 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Take-aki Mitsudo: "Ruthenium Complex-Catalyzed Formation and Cleavage of Carbon-Carbon σ-Bonds. On the Requirement of Highly Qualified Tuning of the Reaction Conditions"Synlett. 3号. 309-321 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Shigeyoshi Sakaki: "Participation of (η^3-Allyl) ruthenium (II) Complexes in C-C Bond Formation and C-C Bond Cleavage. A Theoretical Study"Organometallics. 20・14. 3145-3158 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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