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Ruthenium Complex-Catalyzed Highly Selective Organic Syntheses

Research Project

Project/Area Number 05403024
Research Category

Grant-in-Aid for General Scientific Research (A)

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

WATANABE Yoshihisa  Graduate School of Engineering, Professor, 工学部, 教授 (70025956)

Co-Investigator(Kenkyū-buntansha) WADA Kenji  Graduate School of Engineering, Instructor, 工学部, 助手 (10243049)
KONDO Teruyuki  Graduate School of Engineering, Instructor, 工学部, 助手 (20211914)
MITSUDO Take-aki  Graduate School of Engineering, Professor, 工学部, 教授 (90026344)
Project Period (FY) 1993 – 1994
Project Status Completed (Fiscal Year 1994)
Budget Amount *help
¥33,700,000 (Direct Cost: ¥33,700,000)
Fiscal Year 1994: ¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1993: ¥26,900,000 (Direct Cost: ¥26,900,000)
KeywordsRuthenium complex / Selective organic synthesis / pi-Allylruthenium complex / Ambiphilicity / Formyl C-H activation / Carbonylation / Organometallic catalysis / Reductive N-Heterocyclization / 還元的N-複素環化反応 / 炭素-炭素結合生成反応 / アリル化反応 / 炭素求核剤 / アセチレン / ノルボルネン
Research Abstract

We have been studying on ruthenium complex-catalyzed novel selective organic syntheses, especially from the view point of novel and selective carbon-carbon bond forming reactions. In the present work, ruthenium complex catalyzed novel methods for construction of carbon skeleton via pi-allylruthenium complexes as key intermediates or formyl C-H bond activation, together with the selective organic syntheses using related transition metal complex catalysts, have been developed. This year, 1. we have found that several eta^3-allylruthenium (II) complexes, such as (eta^3-allyl) Ru (OAc) (CO)_3 or cationic (eta^3-allyl) Ru (CO)_3] ^+ (OTf)^-, can function as both a nucleophile and an electrophile, i.e., as an ambiphile. 2. The following ruthenium complex-catalyzed novel transformations of alkyl formates were developed : selective decarbonylation of alkyl formates to alcohols, alkylation of arenes and alkenes using alkyl formates in neutral media, and addition of alcohols to alkenes. 3. Photo-, electro-, and thermal carbonylation of alkyl iodides in the presence of group 7 and 8-10 metal carbonyl catalysts, including ruthenium complexes. 4. In the course of the study on ruthenium complex-catalyzed reactions, we have found that Co_2 (CO)_8-catalyzed ring-opening carbonylation of oxiranes and oxetane smoothly proceeds with high regioselectivity under 1 atm of carbon monoxide at room temperature to give the corresponding beta- and gamma-siloxyamides in high yields, respectively. In addition, the PdCl_2 (PPh_3)_2-SnCl_2 system was found to show high catalytic activity for the reductive N-heterocyclization of nitrobenzenes to indole and 2H-indazole derivatives. The intermolecular reductive N-heterocyclization of 2-nitrobenzaldehyde or 2-nitrophenyl ketones with formamide using PdCl_2 (PPh_3)_2 with MoCl_5 was found to give the corresponding quinazoline derivatives in moderate yields.

Report

(3 results)
  • 1994 Annual Research Report   Final Research Report Summary
  • 1993 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] Teruyuki Kondo: "Photo-,Electro,and Thermal Carbonylation of Alkyl Iodides in the Presence of Group 7 and 8-10 Metal Carbonyl Catalysts" J.Organomet.Chem.473. 163-173 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Teruyuki Kondo: "Ruthenium Complex-Catalyzed Novel Transformation of Alkyl Formates" J.Organomet.Chem.(印刷中). (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Teruyuki Kondo: "Nucleophilic and Electrophilic Allylation Reactions.Synthesis,Structure and Ambiphilic Reactivity of η3-Allylruthenium(II)Complexes" Organometallics. (印刷中). (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Motohiro Akazome: "Complex-Catalyzed Reductive N-Heterocyclization of Nitroarenes:Novel Synthesis of Indole and 2H-Indazole Derivatives" J.Org.Chem.59. 3375-3380 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Motohiro Akazome: "Palladium Complex-Catalyzed Intermolecular Reductive N-Heterocyclization:Novel Synthesis of Quinazoline Derivatives from 2-Nitrobenzaldehyde or 2-Nitrophenyl Ketones with Formamide" J.Organomet.Chem.(印刷中). (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Yoshihisa Watanabe: "Co_2(CO)_8-Catalyzed Ring-Opening Carbonylation of Cyclic Ethers Using N-Silylamines" Bull.Chem.Soc.Jpn.67. 879-882 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Teruyuki Kondo: "Photo-, Electro, and Thermal Carbonylation of Alkyl Iodides in the Presence of Group 7 and 8-10 Metal Carbonyl Catalysts" J.Organomet.Chem.vol.473. 163-173 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Teruyuki Kondo: "Ruthenium Complex-Catalyzed Novel Transformation of Alkyl Formates" J.Organomet.Chem.(in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Teruyuki Kondo: "Nucleophilic and Electrophilic Allylation Reactions. Synthesis, Structure and Ambiphilic Reactivity of eta^3-Allylruthenium (II) Complexes" Organometallics. (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Motohiro Akazome: "Complex-Catalyzed Reductive N-Heterocyclization of Nitroarenes : Novel Synthesis of Indole and 2H-Indazole Derivatives" J.Org.Chem.vol.59. 3375-3380 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Motohiro Akazome: "Palladium Complex-Catalyzed Intermolecular Reductive N-Heterocyclization : Novel Synthesis of Quinazoline Derivatives from 2-Nitrobenzaldehyde or 2-Nitrophenyl Ketones with Formamide" J.Organomet.Chem.(in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Yoshihisa Watanabe: "Co_2 (CO)_8-Catalyzed Ring-Opening Carbonylation of Cyclic Ethers Using N-Silylamines" Bull.Chem.Soc.Jpn.vol.67. 879-882 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] Teruyuki Kondo: "Photo-,Electro,and Thermal Carbonylation of Alkyl Iodides in the Presence of Group 7 and 8-10 Metal Carbonyl Catalysts" J.Organomet.Chem.473. 163-173 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Teruyuki Kondo: "Ruthenium Complex-Catalyzed Novel Transformation of Alkyl Formates" J.Organomet.Chem.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Teruyuki Kondo: "Nucleophilic and Electrophilic Allylation Reactions.Synthesis,Structure and Ambiphilic Reactivity of η3-Allylruthenium(II)Complexes" Organometallics. (印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Motohiro Akazome: "Complex-Catalyzed Reductive N-Heterocyclization of Nitroarenes:Novel Synthesis of Indole and 2H-Indazole Derivatives" J.Org.Chem.59. 3375-3380 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Motohiro Akazome: "Palladium Complex-Catalyzed Intermolecular Reductive N-Heterocyclization:Novel Synthesis of Quinazoline Derivatives from 2-Nitrobenzaldehyde or 2-Nitrophenyl Ketones with Formamide" J.Organomet.Chem.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Yoshihisa Watanabe: "Co_2(CO)_8-Catalyzed Ring-Opening Carbonylation of Cyclic Ethers Using N-Silylamines" Bull.Chem.Soc.Jpn.67. 879-882 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Shi-Wei Zhang: "Ruthenium complex-catalyzed allylic alkylation of carbonucleophiles with allylic carbonates" Journal of Organometallic Chemistry. 450. 197-207 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Take-aki Mitsudo: "[2+2]Cross-addition of norbornenes with alkynes catalyzed by ruthenium complexes" Angewandte Chemie. (in press). (1994)

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2016-04-21  

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