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1999 Fiscal Year Final Research Report Summary

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
KeywordsTransition metal complex catalysts / Catalytic carbon bond formation / Carbocycle synthesis / Ruthenium complex catalysts / Rhodium complex catalysts / Palladium complex catalysts / Organotitanium reagents / Carbonylation
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.

  • Research Products

    (40 results)

All Other

All Publications (40 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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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

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Published: 2001-10-23  

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