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Synthetic application of carbon-carbon bond formations induced by group 9 metal catalyzed multi-component couplings

Research Project

Project/Area Number 13450368
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

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) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥13,000,000 (Direct Cost: ¥13,000,000)
Fiscal Year 2003: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2002: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2001: ¥7,700,000 (Direct Cost: ¥7,700,000)
Keywordsrhodium complexes / CO incorporation / silylative cyclocarbonylation / lactone formation / lactam formation / allylic substitution / iridium complexes / propargylic substitution / シリルホルミル化 / 位置選択的アリル位置換 / 双環性ケトン骨格形成 / 分子内シリルカルバモイル化 / 光学活性δ-ラクタム環形成 / 環化シリルホルミル化 / 環化ヒドロカルボニル化 / 渡環的遠隔シリルホルミル化 / 渡環的遠隔ヒドロシリル化 / Mannich型三成分カップリング / イリジウム(I)カチオン錯体 / プロパルギル位置換反応
Research Abstract

This project focuses the development of carbon-carbon bond formation on the basis of multi-component coupling catalyzed by group 9 metal complex in one-pot procedure. Along the proposed strategy on rhodium-catalyzed reactions we successfully obtained the following results ; (1) the formation of bicyclo[3.3.0]octenone frameworks by the one-pot reactions among a hydrosilane, a 1,6-diyne, and CO and its application to the synthesis of hirsutene, (2) exploitation of a new method for the construction of 4,5, and 6-membered lactones by the incorporation of CO into alkynylalcohols and transformation of spiro-type γ-lactones to bicyclic ketones, (3) exploitation of a new method for the construction of 4,5,6, and 7-membered lactams by the incorporation of CO into alkynylamines, and (4) annulative long range silylformylation of hept-1-ene-6-ynes. We also realized a new three-component coupling under neutral conditions as follows ; formal hydrocarbamoylation and hydroallylation toward electron-deficient alkenes and a new Mannich type coupling triggered by the oxydative addition of a hydrosilane to low-valent rhodium metal. It was also revealed that an Ir-cationic complex shows strong Lewis acidity in CH_2Cl_2 and behaves as an efficient catalyst for aldol coupling, Michael type coupling, direct substitution of allylic alcohols and selective substitution of propargylic esters in reactions involving enoxy silane as a nucleophile.

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] Yukimasa Fukuta: "Synthesis of 3-Silyl-2(5H)-furanone by Rhodium-catalyzed Cyclocarbonylation"Tetrahedron Letters. 42. 1301-1304 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takako Muraoka: "Rhodium-Catalyzed Formal Hydrocarbamoylation toward an α,β-Unsaturated Carbonyl Compound Using Aryl Isocyanate and Hydrosilane"Organometallics. 20. 4676-4682 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Isamu Matsuda: "Carbon-carbon Bond Formation by Reactions of Allylic Alcohol with Enoxysilane in the Presence of Ir-complex"Tetrahedron Letters. 43. 1043-1046 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takako Muraoka: "Rhodium-Catalyzed Approach to Mannich-type Products Using Aldimine,α,β-Unsaturated Ester, and Hydrosilane"Chemical Communications. 1284-1285 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takako Muraoka: "Rhodium-Catalyzed Silylative Cyclization of 1,6-Heptadiyne Derivatives : A Versatile Route for the Synthesis of a 1,2-Dialkylidene-cyclopentane Skelton"Organometallics. 21. 3650-3660 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Isamu Matsuda: "Ir-Catalyzed Substitution of propargylic-type Esters with Enoxysilanes"J. American Chemical Society. 124. 9072-9073 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 松田 勇: "低原子価ロジウム錯体へのヒドロシランの酸化的付加を基点とする炭素-炭素結合形成反応の開発"有機合成化学協会誌. 61. 123-132 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Yukimasa Fukuta: "Synthesis of 3-Silyl-2(5H)-furanone by Rhodium-catalyzed Cyclocarbonylation"Tetrahedron Letters. 42-7. 1301-1304 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takako Muraoka: "Rhodium-Catalyzed Formal Hydrocarbamoylation toward an α,β-Unsaturated Carbonyl Compound Using Aryl Isocyanate and Hydrosilane"Organometallics. 20-22. 4676-4682 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Isamu Matsuda: "Carbon-carbon Bond Formation by Reactions of Allylic Alcohol with Enoxysilane in the Presence of Ir-complex"Tetrahedron Letters. 43-6. 1043-4046 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takako Muraoka: "Rhodium-Catalyzed Approach to Mannich-type Products Using Aldimine, α,β-Unsaturated Ester, and Hydrosilane"Chemical Communications. No.12. 1284-1285 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Takako Muraoka: "Rhodium-Catalyzed Silylative Cyclization of 1,6-Heptadiyne Derivatives : A Versatile Route for the Synthesis of a 1,2-Dialkylidene-cyclopentane Skeleton"Organometallics. 21-17. 3650-3660 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Isamu Matsuda: "Ir-Catalyzed Substitution of propargylic-type Esters with Enoxysilanes"J.American Chemical Society. 124-31. 9071-8073 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Isamu Matsuda: "Design of Carbon-Carbon Bond Forming Reactions Starting from the Oxidative Addition of a Hydrosilane to a Rh(I) Complex"Journal of Synthetic Organic Chemistry, Japan. 61-2. 123-132 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 松田 勇, 小森健一, 伊藤健兒: "Ir-Catalyzed Substitution of Propargylic-type Esters with Enoxysilanes"J. Am. Chem. Soc.. 124巻・31号. 9072-9073 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 村岡貴子, 松田 勇, 伊藤健兒: "Rhodium-Catalyzed Silylative Cyclization of 1,6-Heptadiyne Derivatives : A Versatile Route for the Synthesis of a 1,2-Dialkylidenecyclopentane Skeleton"Organometallics. 21巻・17号. 3650-3660 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 松田 勇: 有機合成化学協会誌. 61巻・2号. 123-132 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 村岡貴子, 松田 勇, 伊藤健兒: "Rhodium-Catalyzed Formal Hydrocarbamoylation toward an α, β-Unsaturated Carbonyl Compound Using Aryl Isocyanate and Hydrosilane"Organometallics. 20巻22号. 4676-4682 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 松田 勇, 若松章吾, 小森健一, 牧野竜也, 伊藤健兒: "Carbon-Cabon Bond Formation by Reactions of Allylic Alcohol with Enoxysilane in the Presence of Ir-complex"Tetrahedron Letters. 43巻6号. 1043-1046 (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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