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1997 Fiscal Year Final Research Report Summary

Highly reactive and selective olefin carbometalation

Research Project

Project/Area Number 08454196
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

NAKAMURA Eiichi  The University of Tokyo Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (00134809)

Project Period (FY) 1996 – 1997
Keywordsallyl metal / hydrazone / carbometalation / organocuprate / computational study / asymmetric synthesis
Research Abstract

Addition of an organometallic reagent to an isolated olefin (olefin carbometalation reaction) is not only of synthetic interest but of mechanistic interest. Although the organometallic addition of carbonyl compounds has been a well-established chemistry, the olefin carbometalation reaction has been developed in rather limited araea owing to the lack of substantial p information on the reaction mechanism of the carbometalation reaction. In this reset, we developed new carbometalation reactions by using highly reactive and selective reagents. The experimental and theoretical results are listed below.
(1) Theoretical studies on the addition of polymetallic lithium organocuprate clusters to C-Cmultiple bonds was carried out with ab initio and density functional calculation. This study firstly provided detailed mechanisms of carfbocupration and 1,4-addition reaction, and revealed importance of cluster structure of the reagent.
(2) Highly enantioselective addition of organometallic reagent to C=N double bond was achieved by using optically active allylic zinc reagents which were developed during the study on enantioselective carbometalation reaction of an isolated olefin.
(3) Addition of metal enolate species to cyclopropenone acetal have been found in the course of the study on the olefin carbometalation reaction. The carbometalation product, cyclopropyl metal, was trapped by various electrophile. This is the first example of the addition of metal enolate to olefin and utilization of the intermediate organometallic species.

  • Research Products

    (10 results)

All Other

All Publications (10 results)

  • [Publications] E.Nakamura: "Carbometalation of Cyclopropene.Diastereoselective cis-Addition of Zincated Amides,Esters and Hydrazones" J.Org.Chem.62. 792-793 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E.Nakamura: "Unusually Stable Organomercury Hydrides and Radical" Angew.Chem.Int.Ed.Engl.36. 374-376 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Nakamura: "Allylzincation of Z-Aldimines.Enantioselective Allylzincation of Z-aldimines in the Presence of Anionic Bis-oxazoline." J.Am.Chem.Soc.118. 8489-8490 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E.Nakamura: "Theoretical Studies on the Addition of Polymetallic Lithium Organocuprate Cluster to Acetylene." J.Am.Chem.Soc.119. 4887-4899 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E.Nakamura: "Reaction Pathway of Conjugate Addition of Lithium Organocuprate Clusters to Acrolein" J.Am.Chem.Soc.119. 4900-4910 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E.Nakamura: "Carbometalation of Cyclopropene. Diastereoselective cis-Addition of Zincated Amides, Esters and Hydrazones" J.Org.Chem.62. 792-793 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E.Nakamura: "Unusually Stable Organomercury Hydrides and Radicals" Angew.Chem.Int.Ed.Engl.36. 374-376 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Nakamura: "Allylzincation of Z-Aldimines. Enantioselective Allylzincation of Z-aldimines in the Presence of Anionic Bis-oxazoline." J.Am.Chem.Soc.118. 8489-8490 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E.Nakamura: "Theoretical Studies on the Addition of Polymetallic Lithium Organocuprate Clusters to Acetylene." J.Am.Chem.Soc.119. 4887-4889 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E.Nakamura: "Reaction Pathway of Conjugate Addition of Lithium Organocuprate Clusters to Acrolein" J.Am.Chem.Soc.119. 4900-4910 (1997)

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

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Published: 1999-03-16  

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