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A New Approach to the Construction of Carbon Framework Using Metallacumulene Derivatives

Research Project

Project/Area Number 16350059
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionWaseda University

Principal Investigator

SHIBATA Takanori  Waseda University, Faculty of Science and Engineering, Professor (80265735)

Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥13,300,000 (Direct Cost: ¥13,300,000)
Fiscal Year 2006: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 2005: ¥4,500,000 (Direct Cost: ¥4,500,000)
Fiscal Year 2004: ¥6,700,000 (Direct Cost: ¥6,700,000)
KeywordsOrganic Synthesis / Complex Catalysts / Transition Metals / Asymmetric Synthesis / Cycloaddition / Cyclic Compounds / Chirality / 選択的合成・反応 / 有機金属触媒 / ファインケミカルズ / 集積型多重結合 / ブタトリエン / エノラート / アルドール反応 / アシルシラン
Research Abstract

There are many reactions of 1, 2-propadienes(allenes), which have cumulated double bond moieties, as unique synthetic reagents. Among them, the features of the cumulated double bond are effectively utilized, that cannot be achieved by simple double or triple bond. In this research, I recognize vinylidene and allenylidene complexes as metal analogue of 1, 2-propadienes and 1, 2, 3-butatriene, respectively, and pay attention to the reactivity of carbon-carbon double bond in metallacumulenes. I plan to search for synthetic reactions that make the best use of their characteristics, and that use metallacumulenes as two or three carbon unit.
I first examined the synthesis of vinylidene complexes from rhodium and iridium ones, which are known to be relatively electron-rich metals. According to the conventional methods, I tried to prepare them from low valent rhodium complexes and terminal alkynes via isomerization along with a hydrogen transfer. I failed but obtained multicyclic compounds by cycloaddition of alkyne moieties. Thus, I focused on the development of low valent late transition metal catalyzed-cycloaddition of alkynes and alkenes, especially enantioselective reaction using chiral metal catalysts.
For example, transition metal-catalyzed[2+2+2] cycloaddition is a well-established protocol for the construction of six-membered ring systems. I developed a new type of enantioselective[2+2+2] cycloaddition for the synthesis of quaternary carbon stereocenters. The intramolecular reaction of various 1, 4-diene-ynes proceeded using a chiral rhodium catalyst and tricyclic compounds possessing a strained bicyclo[2.2.1] heptene skeleton or bicyclic cyclo-1, 3-dienes were obtained, depending on the substituent on the 1, 4-diene moiety.

Report

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

    (46 results)

All 2007 2006 2005 2004 Other

All Journal Article (34 results) (of which Peer Reviewed: 14 results) Presentation (11 results) Remarks (1 results)

  • [Journal Article] Rh-Catalyzed Cyclization of Diynes and Enynes Initiated by Carbonyl-Directed Activation of Aromatic and Vinylic C-H Bonds2007

    • Author(s)
      K.Tsuchikama, Y.Kuwata, Y.Tahara, Y.Yoshinami, and T.Shibata
    • Journal Title

      Organic Letters 9

      Pages: 3097-3099

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Enantioselective [2+2+2] Cycloaddition of Endiynes for the Synthesis of Chiral Cyclohexa-1,3-dienes2007

    • Author(s)
      T.Shibata, H.Kurokawa, and K.Kanda
    • Journal Title

      Journal of Organic Chemistry 72

      Pages: 6521-6525

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Rh-Catalyzed Cyclization of Diynes and Enynes Initiated by Carbonyl-Directed Activation of Aromatic and Vinylic C-H Bonds2007

    • Author(s)
      K. Tsuchikama, Y. Kuwata, Y. Tahara, Y. Yoshinami, T. Shibata
    • Journal Title

      Org. Lett. 9

      Pages: 3097-3099

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enantioselective[2+2+2] Cycloaddition of Endiynes for the Synthesis of Chiral Cyclohexa-1,3-dienes2007

    • Author(s)
      T. Shibata, H. Kurokawa, K. Kanda
    • Journal Title

      J. Org. Chem. 72

      Pages: 6521-6525

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Rh-Catalyzed Enantioselective [2+2] Cycloaddition of Alkynyl Esters and Norbornene Derivatives2006

    • Author(s)
      T.Shibata, K.Takami, and A.Kawachi
    • Journal Title

      Organic Letters 8

      Pages: 1343-1345

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Enantioselective Intramolecular [2+2+2] Cycloaddition of 1,4-Diene-ynes:A New Approach to the Construction of Quaternary Carbon Stereocenters2006

    • Author(s)
      T.Shibata, Y.Tahara
    • Journal Title

      Journal of American Chemical Society 128

      Pages: 11766-11767

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Highly Enantioselective Construction of a Chiral Spirocyclic Structure by the [2+2+2] Cycloaddition of Diynes and exo-Methylene Cyclic Compounds2006

    • Author(s)
      K.Tsuchikama, Y.Kuwata, T.Shibata
    • Journal Title

      Journal of American Chemical Society 128

      Pages: 13686-13687

    • 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
    • Peer Reviewed
  • [Journal Article] イリジウム、ロジウム錯体を用いる触媒的付加環化反応の開発2006

    • Author(s)
      柴田 高範
    • Journal Title

      有機合成化学協会誌 64

      Pages: 913-9221

    • NAID

      10018052266

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Recent Advances in the Catalytic Pauson-Khand-Type Reaction2006

    • Author(s)
      T.Shibata
    • Journal Title

      Advanced Synthesis & Catalysis 348

      Pages: 2328-2336

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Rh-Catalyzed Enantioselective[2+2] Cycloaddition of Alkynyl Esters and Norbomene Derivatives2006

    • Author(s)
      T. Shibata, K. Takami, A. Kawachi
    • Journal Title

      Org. Lett. 8

      Pages: 1343-1345

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enantioselective Intramolecular[2+2+2] Cycloaddition of 1,4-Diene-ynes : A New Approach to the Construction of Quatemary Carbon Stereocenters2006

    • Author(s)
      T. Shibata, Y. Tahara
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 11766-11767

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Highly Enantioselective Construction of a Chiral Spirocyclic Structure by the[2+2+2] Cycloaddition of Diynes and exo-Methylene Cyclic Compounds2006

    • Author(s)
      K. Tsuchikama, Y., T. Shibata
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 13686-13687

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Iridium and Rhodium Complex-Catalzed Cycloadditions2006

    • Author(s)
      T. Shibata
    • Journal Title

      J. Syn. Org. Chem. Jpn. 64

      Pages: 913-9221

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Recent Advaces in the Catalytic Pauson-Khand-Type Reaction2006

    • Author(s)
      T. Shibata
    • Journal Title

      Adv. Syn & Cat. 348

      Pages: 2328-2336

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Rh-Catalyzed Enantioselective[2+2] Cycloaddition of Alkynyl Esters and Norbornene Derivatives2006

    • Author(s)
      T.Shibata, K.Takami, A.Kawachi
    • Journal Title

      Organic Letters 8

      Pages: 1343-1345

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Enantioselective INtramolecular [2+2+2] Cycloaddition of 1,4-Diene-ynes : A New Approach to the Construction of Quaternary Carbon Stereocenters2006

    • Author(s)
      T.Shibata, Y.Tahara
    • Journal Title

      Journal of American Chemical Society 128

      Pages: 11766-11767

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Cationic Platinum-Catalyzed Etherification by Intra- and Intermolecular Dehydration of Alcohols2005

    • Author(s)
      T.Shibata, R.Fujiwara, and Y.Ueno
    • Journal Title

      Synlett

      Pages: 152-154

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Iridium-Catalyzed Enantioselective Cycloisomerization of Nitrogen-bridged 1,6-Enynes to 3-Azabicylo[4.1.0]heptenes2005

    • Author(s)
      T.Shibata, Y.Kobayashi, S.Maekawa, N.Toshida, and K.Takagi
    • Journal Title

      Tetrahedron 61

      Pages: 9018-9024

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Iridium-Catalyzed Enantioselective Pauson-Khand-type Reaction of 1,6-Enynes2005

    • Author(s)
      T.Shibata, N.Toshida, M.Yamasaki, S.Maekawa, and K.Takagi
    • Journal Title

      Tetrahedron 61

      Pages: 9974-9979

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Enantioselective Construction of Quaternary Carbon Centers by Catalytic [2+2+2] Cycloaddition of 1,6-Enynes and Alkynes2005

    • Author(s)
      T.Shibata, Y.Arai, and Y.Tahara
    • Journal Title

      Organic Letters 7

      Pages: 4955-4957

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Cationic Platinum-Catalyzed Etherification by Intra-and Intermolecular Dehydration of Alcohols2005

    • Author(s)
      T. Shibata, R. Fujiwara, Y. Ueno
    • Journal Title

      Synlett

      Pages: 152-154

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Iridium-Catalyzed Enantioselective Cycloisomerization of Nitrogen-bridged 1,6-Enynes to 3-Azabicylo[4.1.0] heptenes2005

    • Author(s)
      T. Shibata, Y. Kobayashi, S. Maekawa, N. Toshida, K. Takagi
    • Journal Title

      Tetrahedron 61

      Pages: 9018-9024

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Iridium-Catalyzed Enantioselective Pauson-Khand-type Reaction of 1,6-Enynes2005

    • Author(s)
      T. Shibata, N. Toshida, M. Yamasaki, S. Maekawa, K. Takagi
    • Journal Title

      Tetrahedron 61

      Pages: 9974-9979

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enantioselective Construction of Quaternary Carbon Centers by Catalytic[2+2+2] Cycloaddition of 1,6-Enynes and Alkynes2005

    • Author(s)
      T. Shibata, Y. Arai, Y. Tahara
    • Journal Title

      Org. Lett. 7

      Pages: 4955-4957

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Enantioselective Construction of Quaternary Carbon Centers by Catalytic [2+2+2] Cycloaddition of 1,6-Enynes and Alkynes2005

    • Author(s)
      Takanori Shibata, Yoshikazu Arai, Yu-ki Tahara
    • Journal Title

      Organic Letters 7

      Pages: 4955-4957

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Chemo- and Regioselective Intramolecular Hydrosilylative Carbocyclization of Allenynes2004

    • Author(s)
      T.Shibata, S.Kadowaki, and K.Takagi
    • Journal Title

      Organometallics 23

      Pages: 4116-4120

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Iridium Complex-Catalyzed Intramolecular Ene-Type Reaction of 1,6-Enynes Accelerated in Ionic Liquid2004

    • Author(s)
      T.Shibata, M.Yamasaki, S.Kadowaki, and K.Takagi
    • Journal Title

      Synlett

      Pages: 2812-2814

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] The Reaction of Butatrienolates with Aldehydes for the Syntheses of α-Vinylidene Acylsilanes2004

    • Author(s)
      T.Shibata, K.Takami, Y.Arai, and K.Tsuchikama
    • Journal Title

      Bulletin of the Chemical Society of Japan 77

      Pages: 1937-1938

    • NAID

      10013738022

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Chemo-and Regioselective Intramolecular Hydrosilylative Carbocyclization of Allenynes2004

    • Author(s)
      T. Shibata, S. Kadowaki, K. Takagi
    • Journal Title

      Orgunometullics 23

      Pages: 4116-4120

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Iridium Complex-Catalyzed Intramolecular Ene-Type Reaction of 1,6-Enynes Accelerated in Ionic Liquid2004

    • Author(s)
      T. Shibata, M. Yamasaki, S. Kadowaki, K. Takagi
    • Journal Title

      Synlett

      Pages: 2812-2814

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The Reaction of Butatrienolates with Aldehydes for the Syntheses of cr-Vinylidene Acylsilanes2004

    • Author(s)
      T. Shiata, K. Takami, Y. Arai, K. Tsuchikama
    • Journal Title

      Bull. Chem. Soc. Jpn. 77

      Pages: 1937-1938

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Chemo-and Regioselective Intramolecular Hydrosilylative Carbocyclization of Allenynes2004

    • Author(s)
      T.Shibata, S.Kadowaki, K.Takagi
    • Journal Title

      Organometallics 23

      Pages: 4116-4120

    • Related Report
      2004 Annual Research Report
  • [Journal Article] The Reaction of Butatrienolates with Aldehydes for the Syntheses of a-Vinylidene Acylsilanes2004

    • Author(s)
      T.Shibata, K.Takami, Y.Arai, K.Tsuchikama
    • Journal Title

      Bulletin of Chemical Society Japan 77

      Pages: 1937-1938

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Iridium Complex-Catalyzed Intramolecular Ene-Type Reaction of 1,6-Enynes Accelerated in Ionic Liquid2004

    • Author(s)
      T.Shibata, M.Yamasaki, S.Kadowaki, K.Takagi
    • Journal Title

      Synlett

      Pages: 2812-2814

    • Related Report
      2004 Annual Research Report
  • [Presentation] Enantioselective Intramolecular Cycloaddition of 1,4-Diene-ynes for the Construction of Quaternary Carbon Centers2006

    • Author(s)
      T.Shibata
    • Organizer
      American Chemical Society 232nd National Meeting
    • Place of Presentation
      San Francisco
    • Year and Date
      2006-09-11
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] Enantioselective Intramolecular Cycloadditign of 1,4-Diene-ynes for the Construction of Quaternary Carbon Centers2006

    • Author(s)
      T. Shibata
    • Organizer
      American Chemical Society 232nd National Meeting
    • Place of Presentation
      San Francisco
    • Year and Date
      2006-09-11
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] Iridium Complex-Catalyzed Enantioselective[2+2+2] Cycloaddition for the Synthesis of Axially Chiral Compounds2005

    • Author(s)
      T. Shibata
    • Organizer
      International Chemical Congress of Pacific Basin Society
    • Place of Presentation
      Hawaii,U.S.A
    • Year and Date
      2005-12-17
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] Enantioselective [2+2+2] Cycloaddition for the Construction of Axially Chirality and Quaternary Carbon Stereocenter2005

    • Author(s)
      T.Shibata
    • Organizer
      The Singapore International Chemical Conference 4
    • Place of Presentation
      Singapore
    • Year and Date
      2005-12-09
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] Enantioselective[2+2+2] Cycloaddition for the Construction of Axially Chirality and Quaternary Carbon Stereocenter2005

    • Author(s)
      T. Shibata
    • Organizer
      The Singapore International Chemical Conference 4 Singapore
    • Year and Date
      2005-12-09
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] 触媒的不斉付加環化反応による光学活性化合物の合成2005

    • Author(s)
      柴田 高範
    • Organizer
      高立体選択的有機合成の最前線
    • Place of Presentation
      東京工業大学
    • Year and Date
      2005-12-02
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] 触媒的不斉付加環化反応を利用した光学活性環状化合物の効率的合成2005

    • Author(s)
      柴田 高範
    • Organizer
      第96回 触媒討論会
    • Place of Presentation
      熊本大学
    • Year and Date
      2005-09-23
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] イリジウム触媒を用いる付加環化反応の開発2005

    • Author(s)
      柴田 高範
    • Organizer
      第22回有機合成化学夏季大学
    • Place of Presentation
      高山市民会館
    • Year and Date
      2005-09-06
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] イリジウム、ロジウム触媒による付加環化反応2005

    • Author(s)
      柴田 高範
    • Organizer
      Organometallic Seminar
    • Place of Presentation
      東京農工大学
    • Year and Date
      2005-06-25
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] Iridium Complex-Catalyzed [2+2+2] Cycloaddition for the Synthesis of Axially Chiral Compounds2004

    • Author(s)
      T.Shibata
    • Organizer
      The International Symposium on Catalysis and Fine Chemicals
    • Place of Presentation
      Hong Kong
    • Year and Date
      2004-12-12
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Presentation] Iridium Complex-Catalyzed[2+2+2] Cycloaddition for the Synthesis of Axially Chiral Compounds2004

    • Author(s)
      T. Shibata
    • Organizer
      The International Symposium on Catalysis and Fine Chemicals
    • Place of Presentation
      Hong Kong
    • Year and Date
      2004-12-12
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Remarks] 「研究成果報告書概要(和文)」より

    • URL

      http://www.chem.waseda.ac.jp/shibata/

    • Related Report
      2006 Final Research Report Summary

URL: 

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

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