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Development of Highly Efficient Organometallic Catalysis for Short-step Assembly of Complex Moleculer Structures

Research Project

Project/Area Number 12450360
Research Category

Grant-in-Aid for Scientific Research (B)

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, Associate Professor, 大学院・工学研究科, 助教授 (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) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥16,600,000 (Direct Cost: ¥16,600,000)
Fiscal Year 2002: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2001: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 2000: ¥8,500,000 (Direct Cost: ¥8,500,000)
KeywordsHomogeneous Catalysis / Ruthenium / Palladium / Rhodium / Iridium / Multicomponent Coupling / Organometallic Complex / 触媒的炭素結合形成 / 触媒的付加環化 / メタラサイクル中間体 / ルテニウム錯体触媒 / ロジウム錯体触媒 / イリジウム錯体触媒 / 複素環合成 / パラジウム錯体触媒 / ピリジン骨格合成 / メタラシクペンタジエン
Research Abstract

1. In the presence of catalytic amounts of Cp*Ru(cod)Cl, unsymmetrical 1,6-diynes possessing a variety of functional groups reacted with electron-deficient tricarbonyl compounds at the ketone C=0 double bonds to selectively afford dienones via electrocyclic ring opening of the expected α-pyrans.
2. The Pd(0)-catalyzed cyclization of electron-deficient diynes and triynes efficiently gave polycyclic aromatic coupounds. Their reaction mechanism was elucidated by means of the characterization of relevant intermediate complexes and density functional calculations of intermediate models.
3. A rhodium-catalyzed method for the synthesis of β-amino esters was accomplished in a one-pot procedure from aldimine, α,β-unsaturated ester and hydosilane.
4. Propargylic-type acetates react readily with enoxysilanes in the presence of a catalytic amount of a cationic iridium complex to give β-alkynyl ketones in high to excellent yields. Substitution at propargyl carbon proceeds exclusively or selectively in most types of propargylic esters. Alternatively, the formation of the allenyl products is predominant in the reaction of esters, which have two phenyl groups on the propargyl carbon.

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (29 results)

All Other

All Publications (29 results)

  • [Publications] Yoshihiko Yamamoto, Tatsuya Ohno, Kenji Itoh: "Selective Synthesis of Fused Cyclooctatetraenes by [4+4] Coupling Between Two Different Diene Units"Chemistry -A European Journal. 8・20. 4734-4741 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshihiko Yamamoto, Takuya Ohno, Kenji Itoh: "Single-Step Assembly of a C2-Symmetrical Palladium(IV) Spirocyclic Complex"Angewandte Chemie International Edition. 41・19. 3662-3665 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshihiko Yamamoto, Hideyuki Takagishi, Kenji Itoh: "Ruthenium(II)-Catalyzed [2+2+2] Cycloaddition of 1,6-Diynes with Tricarbonyl Compounds"Journal of the American Chemical Society. 124・24. 6844-6845 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Takako Muraoka, Isamu Matsuda, Kenji Itoh: "Rhodium-Catalyzed Silylative Cyclization of 1,6-Heptadiyne Derivatives : A Versatile Route for the Synthesis of a 1,2-Dialkylidenecyclopentane Skeleton"Organometallics. 21・17. 3650-3660 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Isamu Matsuda, Ken-ichi Komori, Kenji Itoh: "Ir-Catalyzed Substitution of Propargylic-type Esters with Enoxysilanes"Journal of the American Chemical Society. 124・31. 9042-9073 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Takako Muraoka, Isamu Matsuda, Kenji Itoh: "Rhodium-catalyzed approach to Mannich-type products using aldimine, α,β-unsaturated ester, and hydrosilane"Chemical Communications. 12. 1284-1285 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshihiko Yamamoto, Tatsuya Ohno, Kenji Itoh: "Selective Synthesis of Fused Cyclooctatetraenes by [4+4] Coupling Between Two Different Diene Units"Chemistry-A European Journal. 8-20. 4734-4741 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshihiko Yamamoto, Takuya Ohno, Kenji Itoh: "Single-Step Assembly of a C2-Symmetrical Palladium (IV) Spirocyclic Complex"Angewandte Chemie International Edition. 41-19. 3662-3665 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshihiko Yamamoto, Hideyuki Takagishi, Kenji Itoh: "Ruthenium (II)-Catalyzed [2+2+2] Cycloaddition of 1,6-Diynes with Tricarbonyl Compounds"Journal of the American Chemical Society. 124-24. 6844-6845 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Takako Muraoka, Isamu Matsuda, Kenji Itoh: "Rhodium-Catalyzed Silylative Cyclization of 1,6-Heptadiyne Derivatives : A Versatile Route for the Synthesis of a 1,2-Dialkylidenecyclopentane Skeleton"Organometallics. 21-17. 3650-3660 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Isamu Matsuda, Ken-ichi Komori, Kenji Itoh: "Ir-Catalyzed Substitution of Propargyl-type Esters with Enoxysilanes"Journal of the American Chemical Society. 124-31. 9042-9073 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Takako Muraoka, Isamu Matsuda, Kenji Itoh: "Rhodium-catalyzed approach to Mannich-type products using aldimine, α,β-unsaturated ester, and hydrosilane"Chemical Communications. 12. 1284-1285 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yoshihiko Yamamoto, Tatsuya Ohno, Kenji Itoh: "Selective Synthesis of Fused Cyclooctatetraenes by [4 + 4] Coupling Between Two Different Diene Units"Chemistry-A European Journal. 8・20. 4734-4741 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshihiko Yamamoto, Takuya Ohno, Kenji Itoh: "Single-Step Assembly of a C_2-Symmetrical Palladium(IV) Spirocyclic Complex"Angewandte Chemie International Edition. 41・19. 3662-3665 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshihiko Yamamoto, Hideyuki Takagishi, Kenji Itoh: "Ruthenium(II)-Catalyzed [2 + 2 + 2] Cycloaddition of 1,6-Diynes with Tricarbonyl Compounds"Journal of the American Chemical Society. 124・24. 6844-6845 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takako Muraoka, Isamu Matsuda, Kenji Itoh: "Rhodium-Catalyzed Silylative Cyclization of 1,6-Heptadiyne Derivatives : A Versatile Route for the Synthesis of a 1,2-Dialkylidenecyclopentane Skeleton"Organometallics. 21・17. 3650-3660 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Isamu Matsuda, Ken-ichi Komori, Kenji Itoh: "Ir-Catalyzed Substitution of Propargylic-type Esters with Enoxysilanes"Journal of the American Chemical Society. 124・31. 9042-9073 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takako Muraoka, Isamu Matsuda, Kenji Itoh: "Rhodium-catalyzed approach to Mannich-type products using aldimine, α,β-unsaturated ester, and hydrosilane"Chemical Communications. 12. 1284-1285 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Yamamoto, S.Okuda, K.Itoh: "Ruthenium(II)-catalyzed [2 + 2 + 2] cycloaddition of 1,6-diynes with electron-deficient nitriles"Chemical Communications. 12. 1102-1103 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Yamamoto, R.Ogawa, K.Itoh: "Significant Chemo- and Regioselectivities in the Ru(II)-Catalyzed [2+2+2] Cycloaddition of 1,6-Diynes with Dicyanides"Journal of the American Chemical Society. 123・25. 6189-6910 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Yamamoto, H.Takagishi, K.Itoh: "Ruthenium(II)-Catalyzed Cycloaddition of 1,6-Diynes with Isocyanates Leading to Bicyclic Pyridones"Organic Letters. 3・13. 2117-2119 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Yamamoto, H.Takagishi, K.Itoh: "Ruthenium-Catalyzed Cycloaddition of 1,6-Diynes with Isothiocyanates and Carbon Disulfide"Journal of the American Chemical Society. 124・1. 28-29 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Muraoka, I.Matsuda, K.Itoh: "Rhodium-Catalyzed Formal Hydrocarbonylation toward an α,β-Unsaturated Carbonyl Compound Using Aryl Isocyanate and Hydrosilane"Organometallics. 20・22. 4676-4682 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] I.Matsuda, S.Wakamatsu, K.Komori, T.Makino, K.Itoh: "Carbon-carbon bond formation by reactions of allylic alcohol with enoxysilane in the presence of Ir-complex"Tetrahedron Letters. 43・6. 1043-1046 (2002)

    • Related Report
      2001 Annual Research Report
  • [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"Chem.Commun.. 7. 549-550 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "Ru(II)-Catalyzed Cycloaddition of 1,6-Heptadiynes with Alkynes. New Synthetic Potentisl of Ruthenacyclopentatrienes as Biscarbenoids"J.Am.Chem.Soc.. 122・18. 4310-4319 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Muraoka,Takako: "Regiodefined Apparent Hydroallylation toward α,β-Unsaturated Carbonyl Compounds Attained by Rhodium-Catalyzed One-pot Procedure."J.Am.Chem.Soc.. 122・39. 9552-9553 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Muraoka,Takako: "Rodium-catalyzed substitution of allylic carbonates with enoxysilanes"Tetrahedron Letters. 41・45. 8807-8811 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Yamamoto,Yoshihiko: "The First Palladium (0) Complex of Linear 1,6,11-Triyne.A Reactive Intermediate in the Catalytic Cyclocotrimerization of Triyne"Organometallics. 19・13. 2403-2405 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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