• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to project page

1998 Fiscal Year Final Research Report Summary

Organic Reactions Directed toword Organic Synthesis by the New Function of Highly Coordinated Transition Metal Complexes

Research Project

Project/Area Number 09640706
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 物質変換
Research InstitutionUniversity of Tsukuba

Principal Investigator

HOJO Makoto  University of Tsukuba, Associate Professor, 化学系, 助教授 (50229150)

Co-Investigator(Kenkyū-buntansha) HOSOMI Akira  University of Tsukuba, Professor, 化学系, 教授 (00004440)
Project Period (FY) 1997 – 1998
Keywordsmanganese / chromium / ate complex / thiomethyl / allyl / propargyl / enolate
Research Abstract

Among transition metal ate complexes, the organocuprates have been predominantly investigated and utilized in organic synthesis, and reactions using these species are mainly based on their alkylating abilities. The reduction rarely takes place as a side reaction in these alkylations. This reductive nature of cuprates has been utilized for the direct generation of organocopper reagents in the cases where only a reductive process occurs. The organomanganese reagents were also reported to be alkylating agents. We found the generation of the enolates from the carbonyl compounds bearing a leaving group such as an acetoxy, siloxy, or halogen group at the a position by using the organomanganese(II) ate complexes and their characteristic reactions with electrophiles. From allyl and propargyl bromides, allyl- and propargylmanganese reagents were generated, and the direct generation of thiomethylmanganese reagents was also attained by the reaction of iodomethylsulfides and the manganese ate complex as a reductant. These reagents reacted with a variety of electrophiles. Chromium ate complexes also behaved as a reductant in the reaction of a-halo ketones and esters to generate chromium enolates that react with carbonyl compounds and alkyl halides efficiently. In the reactions with allyl or propargyl phosphates, the corresponding chromium reagents could be obtained.

  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] M.Hojo: "Di-functionalization of Alkenes Using an Oxidant Generated from Manganese(II) Chloride under Oxygen : Synthesis of γ-Lactones" Heterocycles. 47・1. 97-100 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Hojo: "Reactivity of Rieke Manganese : Synthesis of Pyrrolidine and Piperidine Derivatives" Heterocycles. 49・1. 85-88 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Hojo: "Allenylmethylsilane Derivatives as Synthetic Equivalents of 1,2,3-Butatriene : Synthesis and Reactions of Di-exo-methylenecyclobutanes and -cyclobutenes" Chem.Lett.4. 331-332 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Hojo: "A New Type of Allyl- and Prop-2-ynyl-manganese Species : Generation and Reactions with Electrophiles" J.Chem.Soc.,Chem.Commun.21. 2077-2078 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Hojo: "Manganese Ate Complexes as New Reducing Agents : Perfectly Regiocontrolled Generation and Reactions of the Manganese Enolates with Electrophiles" J.Am.Chem.Soc.119・23. 5459-5460 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Hojo: "A New and Mild System for the Generation of Nonstabilized Carbonyl Ylides : Synthetically Practical Use in Reactions with Electron-Deficient Dipolarophiles" J.Org.Chem.62・25. 8610-8611 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Makoto Hojo: "Manganese Ate Complexes as New Reducing Agents : perfectly Regiocontrolled Generation and Reactions of the Manganese Enolates with Electrophiles" J.Am.Chem.Soc.119 (23). 5459-5460 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Makoto Hojo: "A New Type of Allyl-and Prop-2-ynyl-manganese Species : Generation and Reactions with Electrophiles" J.Chem.Soc.Chem.Commun.2077-2078 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Makoto Hojo: "A New and Mild System for the Generation of Nonstabilized Carbonyl Ylides : Synthetically Practical Use in Reactions with Electron-Deficient Dipolarophiles" J.Org.Chem.62 (25). 8610-8611 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Makoto Hojo: "Di-functionalization of Alkenes Using an Oxidant Generated from Manganese (II) Chloride under Oxygen : Synthesis of gamma-Lactones" Heterocycles. 47 (1). 97-100 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Makoto Hojo: "Allenylmethylsilane Derivatives as Synthetic Equivalents of 1,2,3-Butatriene : Synthesis and Reactions of Di-exo-methylenecyclobutanes and -cyclobutenes" Chem.Lett.331-332 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Makoto Hojo: "Reactivity of Rieke Manganese : Synthesis of Pyrrolidine and Piperidine Derivatives" Heterocycles. 49 (1). 85-88 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Makoto Hojo: "New Reactivity of Methoxyhydridosilane in the Catalytic Activation System" Tetrahedron Lett.40 (5). 911-914 (1999)

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

URL: 

Published: 1999-12-08  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi