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2004 Fiscal Year Final Research Report Summary

Preparation of Organocupper Species Using Silyl Migration and Their Application to Organic Synthesis

Research Project

Project/Area Number 15550085
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionNational University Corporation Tokyo University of Agriculture and Technology

Principal Investigator

TSUBOUCHI Akira  National University Corporation Tokyo University of Agriculture and Technology, Institute of Symbiotic Science and Technology, Research Associate, 大学院・共生科学技術研究部, 助手 (40272637)

Co-Investigator(Kenkyū-buntansha) TAKEDA Takeshi  National University Corporation Tokyo University of Agriculture and Technology, Institute of Symbiotic Science and Technology, Professor, 大学院・共生科学技術研究部, 教授 (40111455)
Project Period (FY) 2003 – 2004
KeywordsSilyl Migration / Peterson Elimination / Vinylcopper / Silicate / Allenes / Enol Silyl Ether
Research Abstract

In this research, preparation methods of organocupper species using O^<sp2>-to-O silyl migration and applications of their organocopper species to organic synthesis were studied. We found that vinylcopper species were readily prepared from vinylsilanes having a hydroxyl group via the 1,3-and 1,4-Brook-type rearrangement by treatment with copper(I) t-butoxide. It was suggested that these reactions were promoted by the combination of the use of copper(I) alkoxides and the formation of silicates by the intramolecular coordination of the alkoxide group. The vinycopper species reacted with various organic halides even in the presence of a proton source to give coupling products. The present silyl rearrangement is applicable to copper(I) enolates prepared from either α-and β-silyl-α,β-unsaturated ketones and copper(I) t-butoxide to produce the vinylcopper species having enol silyl moiety ; by the reaction of the organocopper species with organic halide, the C-C bond formation was achieved with stereoselective formation of the enol silyl ether.
We also demonstrated that allenes were obtained by the Peterson elimination of copper(I) alkoxides of β-triphenylsilylallylic alcohols through the formation of the silicate in the absence of the organic halides. This is the first example of the Peterson elimination at a vinylic position leading to the formation of allenes. The Peterson elimination proceeded even when the β-triphenylsilylallylic alcohols were treated with BuLi by virtue of DMF as a cosolvent. Based on this result, a straightforward carbonyl allenation method was developed by the Pereson olefination of α-lithiovinylsilanes and carbonyl compounds.

  • Research Products

    (3 results)

All 2004

All Journal Article (3 results)

  • [Journal Article] Copper(I) tert-butoxide-promoted coupling of o-(1-hydroxyalkyl)-arylsilanes with organic halides2004

    • Author(s)
      Haruhiko Taguchi
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 429-432

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Copper(I) tert-Butoxide-Promoted Allylation of β-Triphenylsilyl Allylic Alcophols via 1,3-C^<sp2>-to-O Silyl Migration2004

    • Author(s)
      Akira Tsubouchi
    • Journal Title

      Synthesis

      Pages: 1504-1508

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Copper(I) tert-butoxide-promoted coupling of o-(1-hydroxyalkyl)arylsilanes with organic halides2004

    • Author(s)
      Haruhiko Taguchi
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 429-432

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

URL: 

Published: 2006-07-11  

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