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EFFICIENT MOLECULAR CONSTRUCTION BY MULTI-COMPONENT COUPLING REACTIONS IN TRANSITION METAL LIGAND FIELDS

Research Project

Project/Area Number 09305059
Research Category

Grant-in-Aid for Scientific Research (A)

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

Principal Investigator

ITOH Kenji  NAGOYA UNIVERSITY, GRADUATE SCHOOL OF ENGINEERING, PROFESSOR, 大学院・工学研究科, 教授 (60023149)

Co-Investigator(Kenkyū-buntansha) YAMAMOTO Yoshihiko  NAGOYA UNIVERSITY, GRADUATE SCHOOL OF ENGINEERING, ASSISTANT PROFESSOR, 大学院・工学研究科, 助手 (60283412)
MATSUDA Isamu  NAGOYA UNIVERSITY, GRADUATE SCHOOL OF ENGINEERING, ASSOCIATE PROFESSOR, 大学院・工学研究科, 助教授 (80023266)
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥31,700,000 (Direct Cost: ¥31,700,000)
Fiscal Year 1999: ¥6,100,000 (Direct Cost: ¥6,100,000)
Fiscal Year 1998: ¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 1997: ¥19,400,000 (Direct Cost: ¥19,400,000)
KeywordsTransition metal complex catalysts / Catalytic carbon bond formation / Carbocycle synthesis / Ruthenium complex catalysts / Rhodium complex catalysts / Palladium complex catalysts / Organotitanium reagents / Carbonylation / 三成分連結触媒プロセス / ドミノ付加環化 / ラジカル環化 / 1,6-ヘプタジイン / 炭素-炭素結合生成 / 環化反応 / 高次付加環化 / カルボニル環化 / メテニウム錯体 / ロジウム錯体 / ヒドロシリル化 / メチレンラクタム / 有機チタン(III)錯体 / カルボニル / 触媒的付加環化 / 還元カップリング / シリルホルミル化
Research Abstract

1. The aim of this research project is to develop novel transition metal mediated reactions to construct complex molecular structures. The following research results were obtained in active research conducted from 1997 to 2000 fiscal years.
2. (1) Highly selective cross-coupling between 1,6-diynes and linear or cyclic alkenes involving heteroatoms or terminal alkynes in the presence of organoruthenium catalysts by way of metallacyclopentadiene intermediates. Unprecedented new domino couplings of dynes with bicyclic alkenes. (2) Based on the mechanistic aspects of rhodium-catalyzed silylformylation of an alkynes, the construction of cyclopentenones, as well as, four-component coupling of an alkynes, a hydrosilane, carbon monoxide, and pyrrolidine was found. (3) Rhodium-carbonyl catalyzed silylative carbocyclization of 1,6-enynes. (4) Rhodium-catalyzed hydrosilylation of 1,6-diynes and its extension to new catalytic annelation to CィイD260ィエD2 fullerene. (5) Rhodium-catalyzed construction of heterocycles from propargyl alcohols and amines. (6) Iridium-catalyzed Michael and aldol reaction of silylenol ethers. (7) Palladium(0)-catalyzed cyclization between electron-deficient alkynes and diynes and its extension to new triyne cyclization. (8) Novel keto-nitrile coupling and pinacol coupling of dials by means of paramagnetic organization reagents. (9) New cyclooctatetraene synthesis starting from a zircona- and titannametalacyclopentadienes.

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (59 results)

All Other

All Publications (59 results)

  • [Publications] Matsuda, Isamu: "Rhodium Catalyzed Silylformylation of Acetylenic Bonds : Its Scope and Mechanistic Consideration"Organometallics. 16(20). 4327-4345 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "Cp_2TiPh-Coordinated Cyano and Ester Groups as Efficient Ketyl Radical Acceptors in Reductive Radical Cyclization of γ-and δ-Cyanoketones and δ-Ketoesters"J. Chem. Soc., Chem. Commun.. (8). 875-876 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "Ruthenium-Catalyzed Tandem[2+2+2]/[4+2] Cycloaddition of 1, 6-Heptadiyne with Norbornene"Organometallics. 17(10). 1910-1912 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Muraoka, Takako: "Rhodium-Mediated Silylative Cyclization of 1,6-Heptadiynes"Tetrahedron Lett.. 39(40). 7325-7328 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "Cp*Ru(cod)Cl-Catalyzed[2+2+2] Cycloaddition of 1,6-Heptadiynes with Allylic Ethers. A Desisive Role of Coordination to the Ehter Oxygen Atom"J. Org. Chem.. 63(26). 9610-9611 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Matsuda, Isamu: "Rhodium-Catalyzed Intermolecular Silylcarbomoylation of Acetylenic Bonds"Tetrahedron Lett.. 40(13). 2553-2556 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "Ruthenium-Catalyzed Highly Efficient Intramolecular Olefin Coupling of α, ω-Dienes. Facile and Regioselective Synthesis of exo-Methylenecyclopentanes"J. Org. Chem.. 64(7). 2178-2179 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "The Cp2 TiPh-Mediated Reductive Radical Cyclization of Cyanoketones and Related Efficient Trapping of Ketyl Radicals by Cp2TiPh-Coordinated Polar Double Bonds"J. Org. Chem.. 64(9). 3224-3229

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "Highly trans-selective intramolecular Pinacol coupling of dials catalyzed by bulky Cp2TiPh"Chem. Commun.. (7). 825-826 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Matsuda, Isamu: "Rhodium-catalyzed Tranformation of Propargyl Alcohol Derivatives to 2-Silymethyl-2-alkenals"J. Organometal. Chem.. 574. 133-141 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fukuta, Yukimasa: "Rhodium-Catalyzed Domino Silylformylation Combined with Carbocyclization"Tetrahedron Lett.. 40(25). 4703-4706 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "Pd(0)-Catalyzed Selective [2+2+2] Cycloaddition of Dimethyl Nona-2, 7-diyne-1, 9-diolate Derivatives with Dimethyl Acetylenedicarboxylate"Tetrahedron Lett.. 40(27). 5035-5038 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "Fully Substituted Cyclooctatetraenes Assembled by the [4+4] Cross Coupling of Two Different Diene Units. A Shunting Strategy of Wilke's Coupling Mechanism"Chem. Commun.. (16). 1542-1544 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Matsuda, Isamu: "Synthesis of 2-Silylmethyl-2-alkenals by Rhodium-catalyzed Interaction among 2-Propynylamine, Hydrosilane, and CO"Inorg. Chim. Acta. 296. 72-79 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Itoh, Kenji: "Transition-Metal Catalyzed Multi-Component Carbocyclization and Related Reactions of Bifunctional Molecules"有機合成化学協会誌 (J. Synth. Org. Chem. Jpn.). 57(11). 912-923 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Muraoka, Takako: "Rhodium-catalyzed silylative carbocyclization on C60 sphere"Chem. Commun.. (3). 199-200 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Matsuda, Isamu: "Iridium-catalyzed Cross Aldol Coupling and a New Concept to Form an Ir-Si Species"Tetrahedron Lett.. 41(9). 1405-1408 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Matsuda, Isamu: "A Continuous Michael and Aldol Coupling of α,β-Enones Catalyzed by Iridium Complexes"Tetrahedron Lett.. 41(9). 1409-1412 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "Highly Chemo- and Regioselective [2+2+2] Cross-cyclotrimerization of Unsymmetrical 1,6-Diynes with Terminal Alkynes Catalyzed by Cp*Ru(cod)Cl under Mild Conditions"Chem. Commun.. (7). 549-550 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Yamamoto, Yoshihiko: "New Synthetic Potential of Ruthenacyclopentatrienes as Biscarbenoids in Tamdem Cyclopropanation of Bicycloalkenes, and Heteroatom-assisted Cyclotrimerization"J. Am. Chem. Soc.. 122(印刷中). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] MATSUDA, Isamu: "Rhodium Catalyzed Silylformylation of Acetylenic Bonds : Its Scope and Mechanistic Consideration"Organometallics. 16 (20). 4327-4345 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "CpィイD22ィエD2TiPh-Coordinated Cyano and Ester Groups as Efficient Ketyl Radical Acceptors in Reductive Radical Cyclization of γ-and δ-Cyanoketones and δ-Ketoesters"Chem. Commun. (8). 875-876 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "Ruthenium-Catalyzed Tandem [2 + 2 + 2]/[4 + 2] Cycloaddition of 1,6-Heptadiyne with Norbornene."Organometallics. 17 (10). 1910-1912 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] MURAOKA, Takako: "Rhodium-Mediated Silylative Cyclization of 1,6-Heptadiynes"Tetrahedron Lett.. 39 (40). 7325-7328 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "Cp*Ru(cod)Cl-Catalyzed [2 + 2 + 2] Cycloaddition of 1,6-Heptadiynes with Allylic Ethers. A Decisive Role of Coordination to the Ether Oxygen Atom"J. Org. Chem.. 63 (26). 9610-9611 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] MATSUDA, Isamu: "Rhodium-Catalyzed Intermolecular Silylcarbamoylation of Acetylenic Bonds"Tetrahedron Letts.. 40 (13). 2553-2556 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "The Cp2TiPh-Mediated Reductive Radical Cyclization of Cyanoketones and Related Reactions. Efficient Trapping of Ketyl Radicals by Cp2TiPh-Coordinated Polar Double Bonds"J. Org. Chem.. 64 (9). 3224-3229 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "Ruthenium-Catalyzed Highly Efficient Intramolecular Olefin Coupling of α, ω-Dienes. Facile and Regioselective Synthesis of exo-Methylenecyclopentanes"J. Org. Chem.. 64 (7). 2178-2179 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "Highly trans-selective intramolecular Pinacol coupling of dials catalyzed by bulky Cp2TiPh"Chem. Commun.. (7). 825-826 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] MATSUDA, Isamu: "Rhodium-catalyzed Transformation of Propargyl Alcohol Derivatives to 2-Silylmethyl-2-alkenals"J. Organometal. Chem.. 574. 133-141 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] FUKUTA, Yukimasa: "Rhodium-Catalyzed Domino Silylformylation Combined with Carbocyclization ."Tetrahedron Letts.. 40 (25). 4703-4706 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "Pd(0)-Catalyzed Selective [2 + 2 + 2] Cycloaddition of Dimethyl Nona-2,7-diyne-1, 9-diolate Derivatives with Dimethyl Acetylenedicarboxylate"Tetrahedron Letts.. 40 (27). 5035-5038 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "Fully Substituted Cyclooctatetraenes Assembled by the [4 + 4] Cross Coupling of Two Different Diene Units. A Shunting Strategy of Wilke's Metallacyclopentadiene Coupling Mechanism"Chem. Commun.. (16). 1542-1544 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] MATSUDA, Isamu: "Synthesis of 2-Silylmethyl-2-alkenals by Rhodium-catalyzed Interaction among 2-Propynylamine, Hydrosilane, and CO."Inorg. Chim Acta. 296. 72-79 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] ITOH, Kenji: "Transition-Metal Catalyzed Multi-Component Carbocyclization and Related Reactions of Bifunctional Molecules"J. Synth. Org. Chem. Jpn.. 57 (11). 912-923 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] MURAOKA, Takako: "Rhodium-catalyzed silylative carbocyclization on C60 sphere"Chem. Commun.. (3). 199-200 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] MATSUDA, Isamu: "Iridium-catalyzed Cross Aldol Coupling and a New Concept to Form an Ir-Si Species"Tetrahedron Letts.. 41 (9). 1405-1408 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] MATSUDA, Isamu: "A Continuous Michael and Aldol Coupling of α, β-Enones Catalyzed by Iridium Complexes"Tetrahedron Letts.. 41 (9). 1409-1412 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "Highly Chemo- and Regioselective [2 + 2 + 2] Cross-cyclotrimerization of Unsymmetrical 1,6-Diynes with Terminal Alkynes Catalyzed by Cp*Ru(cod)Cl under Mild Conditions"Chem. Commun.. (7). 549-550 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] YAMAMOTO, Yoshihiko: "New Synthetic Potential of Ruthenacyclopentatrienes as Biscarbenoids in Tandem Cyclopropanation of Bicycloalkenes, and Heteroatom-assisted Cyclotrimerization of 1,6-Heptadiynes with Heterocyclic Alkenes"J. Am. Chem. Soc.. 122(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Matsuda,Isamu: "Rhodium-Catalyzed Intermolecular Silylcarbamoylation of Acetylenic Bonds."Tetrahedron Letts.. 40(13). 2553-2556 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "The Cp2TiPh-Mediated Reductive Radical Cyclization of Cyanoketones and Related Reactions. Efficient Trapping of Ketyl Radicals by Cp2TiPh-Coordinated Bonds."J.Org.Chem.. 64(9). 3224-3229 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "Ruthenium-Catalyzed Highly Efficient Intramolecular Olefin Coupling of α,ω-Dienes. Facile and Regioselective Synthesis of exo-Methylenecyclopentanes."J.Org.Chem.. 64(7). 2178-2179 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "Highly trans-selective intramolecular Pinacol coupling of dials catalyzed by bulky Cp2TiPh."Chem.Commun.. (7). 825-826 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Matsuda,Isamu: "Rhodium-catalyzed Tranformation of Propargyl Alcohol Derivatives to 2-Silylmethyl-2-alkenals."J.Organometal.Chem.. 574. 133-141 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "Pd(0)-Catalyzed Selective [2+2+2] Cycloaddition of Dimethyl Nona-2,7-diyne-1,9-diolate Derivatives with Dimethyl Acetylenedicarboxylate."Tetrahedron Letts.. 40(27). 5035-5038 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Fukuta,Yukimasa: "Rhodium-Catalyzed Domino Silylformylation Combined with Carbocyclization"Tetrahedron Letts.. 40(25). 4703-4706 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "Fully Substituted Cyclooctatetraenes Assmbled by the [4+4] Cross Coupling of Two Different Diene Units."Chem.Commun.. (16). 1542-1544 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Matsuda,Isamu: "Synthesis of 2-Silylmethyl-2-alkenals by Rhodium-catalyzed Interaction among 2-Propynylamine,Hydrosilane,and CO."Inorg.Chim Acta.. 296. 72-79 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Itoh,Kenji: "Transition-Metal Catalyzed Multi-Component Carbocyclization and Related Reactions of Bifunctional Molecules"有機合成化学協会誌. 57(11). 912-923 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Muraoka,Takako: "Rhodium-catalyzed silylative carbocyclization on C60 sphere."Chem.Commun.. (3). 199-200 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "Cp^*Ru(cod)Cl-Catalyzed[2+2+2]Cycloaddition of 1,6-Heptadiynes with Allylic Ethers.A Desisive Role of Coordination to the Ether Oxygen Atom" Journal of Organic Chemistry. 63(26). 9610-9611 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Muraoka,Takako: "Rhodium-Mediated Silylative Cyclization of 1,6-Heptadiynes" Tetrahedron Letters. 39(40). 7325-7328 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Nagashima,Hideo: "Multimetallic Activation of Molecular Hydrogen,Leading to Hydrogenation of the Coordinated Azulenes in Di-,Tn-,and Tetranuclear Ruthenium Carbonyl Complexes" Bulletin of Chemical.Society.Japan. 71(10). 2441-2448 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "Ruthenium-Catalyzed Tandem[2+2+2]/[4+2]Cycloaddition of 1,6-Heptadiyne with Norbornene" Organometallics. 17(10). 1910-1912 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "Cp2TiPh-Coordinated Cyano and Ester Groups as Efficient Ketyl Radical Acceptors in Reductive Radical Cyclization of γ- and δ-Cyanoketones and δ-Ketoesters" J.Chem.Soc.,Chem.Commun. 875-876 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 松田勇: "Rhodium-Catalyzed Silylformylation of Acetylenic Bonds : Its Scope and Mechanistic Considerations" Organometallics. 16・20. 4327-4345 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 永嶋英夫: "Carbon-Hydrogen Bond Activation by Triruthenium Cabonyl Species during Cabon Monooxide Promothed Elimination of 4,5-Dihydroacenaphthylene" Bull.Chem.Soc.Jpn.70・9. 2231-2237 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 山本芳彦: "The Cp_2 TiPh-Coordinated Cyano and Ester Groups as an Efficient Ketyl Radical Acceptor in Reductive Radical Cyclization of γ-and δ-Cyanoketones and δ-Ketoesters" J.Chem.Soc.,Chem.Commun.(掲載許可1998年2月24日)(発行予定). (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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