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New Aspect on the Chemistry of Allenes

Research Project

Project/Area Number 16390005
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionKanazawa University

Principal Investigator

MUKAI Chisato  Kanazawa University, Graduate School of Natural Science and Technology, Professor, 自然科学研究科, 教授 (70143914)

Co-Investigator(Kenkyū-buntansha) KITAGAKI Shinji  Kanazawa University, Graduate School of Natural Science and Technology, Associate Professor, 自然科学研究科, 助教授 (20281818)
MIYAKOSHI Naoki  Kanazawa University, Graduate School of Natural Science and Technology, Research, 自然科学研究科, 助手 (00345597)
Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥14,900,000 (Direct Cost: ¥14,900,000)
Fiscal Year 2006: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2005: ¥4,300,000 (Direct Cost: ¥4,300,000)
Fiscal Year 2004: ¥7,000,000 (Direct Cost: ¥7,000,000)
Keywordsallenes / endo-mode cyclization / Pauson-Khand reaction / indoles / indole-2,3-quinodimethane / Hetero-Pauson-Khand reaction / bisallenes / 2,3-quinodimethanes / 環化異性化 / ロジウム / [4+2]環化 / [2+2]環化 / 電子吸引性 / エンド型閉環 / 電子吸引性基 / Pauson-Khand / ロジウム触媒 / 一酸化炭素 / 8員環含酸素複素環化合物 / 中員環構築
Research Abstract

This program has been directed toward development of efficient and novel reactions based on the inherent property of allenes, in particular, the allene possessing an electron-withdrawing group such as a phenylsulfonyl group. As a result, the following several reactions could be developed.
(1) Treatment of 1-phenylsulfonylallene with a proper (co-hydroxy) alkyl side chain at the C,-position with a base afforded the corresponding oxacycles through the endo-mode cyclization process. This novel ring-closing reaction could be applied for the construction of five-to nine-membered oxacycles. The aza-congeners as well as carbocycles were also found to be prepared according to the standard conditions, thus developed. The sulfoxide, phosphine oxide, phosphonate, and ester functionalities were used as an electron-withdrawing group instead a sulfonyl moiety. Furthermore, allenylaniline derivatives provided the corresponding 2,3-disubstituted indoles in an endo-mode ring-closing manner. The allenyla … More niline having a hydroxymethyl group was converted into the indole-2,3-quinodimethane derivative via the intramolecular SN2' reaction.
(2) The Pauson-Khand reaction of allenynes in the presence of Rh catalyst resulted in the efficient formation of bicyclo[4.3.0] as well as bicyclo[5.3.0] skeletons, the latter of which could not be prepared by the Pauson-Khand reaction of enynes. This new-type of Pauson-Khand reaction furnished the bicyclo[6.3.0] framswork as well. Alternatively, the carbodlimide functionality, which is isoelectronic to the allene group, could be successfully used in the Pauson-Khand reaction leading to the efficient construction of pyrrolo[2,3-b]indo1-2-ones.
(3) Reaction of ene-bisallenes, generated from the corresponding propargyl alcohols, underwent the 6π-electrocyclic reaction to afford the quinodimethanes, which were susceptible to the [4+2]cycloaddition reaction with dienophiles. This novel method for the generation of quinodimethane species could be applied for the production of the naphthoquinodimethanes from benzene-bridged bisallene. Interestingly enough, the proper choice of the conditions in the step of bis-allene formation produced the cyclobutene derivatives instead of the [4+2]cycloadducts even if the suitable dienophiles were in existence. Less

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (33 results)

All 2007 2006 2005 2004

All Journal Article (33 results)

  • [Journal Article] Studies of Ring-closing Mode of 4-Hydroxy-2-vinylidenebutanoates : 5- Exo-trig versus 5-Endo-dig.2007

    • Author(s)
      S.Kitagaki
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 1735-1738

    • NAID

      120000809613

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Studies of Ring-closing Mode of 4-Hydroxy-2-vinylidenebutanoates : 5-Exo-trig versus 5-Endo-dig2007

    • Author(s)
      Shinji Kitagaki
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 1735-1738

    • NAID

      120000809613

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Reaction of Ene-bis(phosphinylallenes) : [2+2] versus [4+2] Cycloaddition.2006

    • Author(s)
      S.Kitagaki
    • Journal Title

      Tetrahedron 62

      Pages: 10311-10320

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Intermolecular [4+2] Cycloaddition of o-Quinodimethanes Derived from Ene-bis(sulfinylallenes).2006

    • Author(s)
      S.Kitagaki
    • Journal Title

      J. Org. Chem. 71

      Pages: 6908-6914

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Grubbs Catalyst-mediated Cycloisomerization of Allenenes.2006

    • Author(s)
      C.Mukai
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 3971-3974

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] A Novel Generation of Indole-2,3-quinodimethanes.2006

    • Author(s)
      N.Kuroda
    • Journal Title

      Org. Lett. 8

      Pages: 1843-1845

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Rhodium(I)-Catalyzed Intramolecular Pauson-Khand-Type [2 + 2 + 1] Cycloaddition of Allenenes.2006

    • Author(s)
      F.Inagaki
    • Journal Title

      Org. Lett. 8

      Pages: 1217-1220

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of Naphtho[b]cyclobutenes from 1,2-Bis(3-propynol)benzenes.2006

    • Author(s)
      S.Kitagaki
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 1849-1852

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Co_2(CO)_8-catalyzed Intramolecular Hetero-Pauson-Khand Reaction of Alkynecarbodiimide : Synthesis of (±)-Physostigmine.2006

    • Author(s)
      C.Mukai
    • Journal Title

      Org. Lett. 8

      Pages: 83-86

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Sequential Pericyclic Reaction of Ene-diallenes : An Efficient Approach to the Steroid Skeleton.2006

    • Author(s)
      S.Kitagaki
    • Journal Title

      Org. Lett. 8

      Pages: 95-98

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Reaction of Ene-bis(phosphinylallenes) : [2+2] versus [4+2] Cycloaddition2006

    • Author(s)
      Shinji Kitagaki
    • Journal Title

      Tetrahedron 62

      Pages: 10311-10320

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Shinji Kitagaki2006

    • Author(s)
      Intermolecular [4+2] Cycloaddition of o-Quinodimethanes Derive from Ene-bis(sulfinylallenes)
    • Journal Title

      J. Org. Chem. 71

      Pages: 6908-6914

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Chisato Mukai2006

    • Author(s)
      Grubbs Catalyst-mediated Cycloisomerization of Allenenes
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 3971-3974

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Norikazu Kuroda2006

    • Author(s)
      A Novel Generation of Indole-2, 3-quinodimethanes
    • Journal Title

      Org. Lett. 8

      Pages: 1843-1845

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Fuyuhiko Inagaki2006

    • Author(s)
      Rhodium(I)-Catalyzed Intramolecular Pauson-Khand-Type [2 + 2 + 1] Cycloaddition of Allenenes
    • Journal Title

      Org. Lett. 8

      Pages: 1217-1220

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Rhodium(I)-Catalyzed Intramolecular Pauson-Khand-Type [2+2+1] Cycloaddition of Allenenes.2006

    • Author(s)
      F.Inagaki
    • Journal Title

      Org. Lett. 8

      Pages: 1217-1220

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis of Naphtho[b] cyclobutenes from 1,2-Bis(3-propynol) benzenes.2006

    • Author(s)
      S.Kitagaki
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 1849-1852

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Co_2(CO)_8-Catalyzed Intramolecular Hetero-Pauson-Khand Reaction of Alkynecarbodiimide : Synthesis of (±)-Physostigmine2006

    • Author(s)
      C.Mukai
    • Journal Title

      Organic Letters 8

      Pages: 83-86

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Sequential Pericyclic Reaction of Ene-diallenes : An Efficient Approach to the Steroid Skeleton2006

    • Author(s)
      S.Kitagaki
    • Journal Title

      Organic Letters 8

      Pages: 95-98

    • Related Report
      2005 Annual Research Report
  • [Journal Article] A New Entry to the Synthesis of 2,3-Disubstituted Indoles.2005

    • Author(s)
      C.Mukai
    • Journal Title

      Org. Lett. 7

      Pages: 5793-5796

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Rh(I)-catalyzed Allenic Pauson-Khand Reaction : First Construction of the Bicyclo[6.3.0]undecadienone Ring System.2005

    • Author(s)
      C.Mukai
    • Journal Title

      Tetrahedron 61

      Pages: 10983-10994

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Rh(I)-catalyzed Pauson-Khand Reaction and Cycloisomerization of Allenynes : Selective Preparation of Monocyclic, Bicyclo[m.3.0], and Bicyclo[5.2.0] Ring Systems.2005

    • Author(s)
      C.Mukai
    • Journal Title

      J. Org. Chem. 70

      Pages: 7159-7171

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Preparation of Carbocycles via Base-catalyzed Endo-mode Cyclization of Allenes.2005

    • Author(s)
      C.Mukai
    • Journal Title

      J. Org. Chem. 70

      Pages: 6282-6290

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Total Syntheses of Naturally Occurring Diacetylenic Spiroacetal Enol Ethers.2005

    • Author(s)
      N.Miyakoshi
    • Journal Title

      J. Org. Chem. 70

      Pages: 6045-6052

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Preparation of Carbocycles via Base-Catalyzed Endo-Mode Cyclization of Allenes2005

    • Author(s)
      C.Mukai
    • Journal Title

      The Journal of Organic Chemistry 70

      Pages: 6282-6290

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Rh(I)-Catalyzed Pauson-Khand Reaction and Cycloisomerization of Allenynes : Selective Preparation of Monocyclic, Bicyclo[m.3.0], and Bicyclo[5.2.0] Ring Systems2005

    • Author(s)
      C.Mukai
    • Journal Title

      The Journal of Organic Chemistry 70

      Pages: 7159-7171

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Rh(I)-Catalyzed Allenic Pauson-Khand Reaction : First Construction of the Bicyclo[6.3.0]undecadienone Ring System2005

    • Author(s)
      C.Mukai
    • Journal Title

      Tetrahedron 61

      Pages: 10983-10994

    • Related Report
      2005 Annual Research Report
  • [Journal Article] A New Entry to the Synthesis of 2,3-Disubstituted Indoles2005

    • Author(s)
      C.Mukai
    • Journal Title

      Organic Letters 7

      Pages: 5793-5796

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Base-catalyzed Endo-mode Cyclization of Allenes : Easy Preparation of Five- to Nine-membered Oxacycles.2004

    • Author(s)
      C.Mukai
    • Journal Title

      J. Ore. Chem. 69

      Pages: 6867-6873

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Rh(I)-catalyzed Ring-closing Reaction of Allenynes : Selective Construction of Cycloheptene, Bicyclo[5.3.0]decadienone, and bicyclo[5.2.0]nonene Frameworks.2004

    • Author(s)
      C.Mukai
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 4117-4121

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Construction of Azacycles Based on Endo-mode Cyclization of Allenes.2004

    • Author(s)
      C.Mukai
    • Journal Title

      J.Org.Chem. 69

      Pages: 2128-2136

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Rh(I)-catalyzed ring-closing reaction of allenes : selective construction of cycloheptene, bicyclo[5.3.0]decadienone, and bicyclo[5.2.0]nonene frameworks2004

    • Author(s)
      C.Mukai, F.Inagaki, T.Yoshida, S.Kitagaki
    • Journal Title

      Tetrahedron letters 45

      Pages: 4117-4121

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Base-Catalyzed Endo-Mode Cyclization of Allenes : Easy Preparation of Five-to Nine-Membered Oxacycles2004

    • Author(s)
      C.Mukai, M.Ohta, H.Yamashita, S.Kitagaki
    • Journal Title

      The Journal of Organic Chemistry 69

      Pages: 6867-6873

    • Related Report
      2004 Annual Research Report

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Published: 2004-04-01   Modified: 2016-04-21  

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