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New Syntheses of Highly Reactive and Functional Organometallic Compounds and its Application to Organic Syntheses

Research Project

Project/Area Number 11554029
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 物質変換
Research InstitutionUniversity of Tsukuba

Principal Investigator

HOSOMI Akira  University of Tsukuba, Chemistry, Professor, 化学系, 教授 (00004440)

Co-Investigator(Kenkyū-buntansha) ITO Hajime  Institute for Molecular Sciences, Assistant, 分子化学研究所, 助手 (90282300)
MIURA Katsukiyo  University of Tsukuba, Chemistry, Lecturer, 化学系, 講師 (20251035)
HOJO Makoto  University of Tsukuba, Chemistry, Lecturer, 化学系, 助教授 (50229150)
TOMINAGA Yoshiori  Nagasaki University, Assistant, 薬学部, 助手 (70100881)
TATEIWA Jun-ichi  University of Tsukuba, Chemistry, Assistant, 化学系, 助手 (30302350)
Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥14,100,000 (Direct Cost: ¥14,100,000)
Fiscal Year 2001: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2000: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1999: ¥7,300,000 (Direct Cost: ¥7,300,000)
KeywordsSi-Cu exchange reaction / Stereoselective synthesis / Carbonyl ylides / Srereocontrol / Samarium-mediated reactions / [3+2] Cycloaddition / O- and N-Containing heterocycles / プロパルギルマンガンアート錯体 / 還元的メタル化反応 / 5配位ケイ素ヒドリド反応剤
Research Abstract

The following results are obtained in this research project.
Acid-Catalyzed Cyclization ofVinylsilanes Bearing an Amino Group. Stereoselective Synthesis ofPyrrolidines
In the presence of an acid catalyst, vinylsilanes bearing an amino group protected by an electron-withdrawing group were smoothly bychzed to 2-(silylmethyl) pyrrolidines. This cyclization was utilized for the Stereoselective synthesis of 2 ndisubstituted pyrrqlidines (n = 3-5).
Radical Cyclization of 1-6-Enynes Using Allylstannanes and New Radical Reactions Using Stannyl Enolates as Radical Transfer Agents
In the presence of AEBN, allyltributylstannanes bearing a radical-stabilizing group at the β-position smoothly reacted with 1,6-enynes to give cyclized products incorporated with the stannyl and allyl groups in moderate to good yields This cyclization is valuable for the synthesis of highly functionalized 5-membered carbocycles and heterocycles The reactions with β-cyanoallylstannane formed a certain amount of bicyclo[4.3. … More 0]non-l-enes along with monocyclized products. The radicaHmtiated reactions of α-halo-esters, -nitriles, and -ketones with stannyl enolates gave the corresponding γ-keto denvatives in moderate to high yields. This homolytic process was applied to the three-component coupling reaction among stannyl enolates, haloalkanes, and electron-deficient alkenes.
Silicon-directed Cyclization of Vinylysilanes : Stereoselective Synthesis of Tetrahydrofurans and Tetrahydropyrans
Silicon-directed Stereoselective syn addition of hydroxy group to olefmic double bond occurs intramolecularly in an acid-catalyzed cyclization of vinylsilanes bearing hydroxy group. The cyclization proceeds by stereospecific syn addition of the hydroxy group Vinylsilanes, (Z)-5-silyl-4-penten-l-ols bearing a substituent on the methylene tether, smoothly undergo the acid-catalyzed cyclization to give trans-2,5-, cis-2,4-, and trans-2,3-disubstituted tetrahydrofurans respectively, with moderate to high stereoselectivitv.
Manganese Ate Species: Generation,and Reactions with Electrophiles
Trialkylmanganese (II) ate reagents, "RMnLi" reacted with iodomethylsulfides to produce thiomethylmanganese reagents, where the manganate serves as a reductant not an alkylation agent. The reductive behavior of trialkylmanganese (II) ate reagents provides a protocol for the direct generation of a new class of reagents thiomethylmanganese reagents with structural variety, and the generated thiomethylmanganese reagents reacted with allyl bromides, enones and aldehydes.
New Method for Introduction of a Silyl Group into α,β-Enones Using a Disilane Catalyzed by a Copper(I) salt.
The reaction of a disilane with a Cu(I) salt efficiently induces cleavage of the Si-Si bond to generate a silyl nucleophile in aprotic polar solvent and its 1,4-addition to α,β-unsaturated enones smoothly proceeds with a catalytic amount of a Cu(I) salt were found. This reaction is successfully applied to hexamethyldisilane to generate a trimethylsilyl nucleophile hitherto not easily accessible.
Unprecedented Manganese-Mediated Reactions : Generation of Non-Stabilized Carbonyl Ylids.
Activated manganese generates nonstabilized carbonyl ylides from bis (chloromethyl) ethers as a precursor, and using this system with manganese as a reductant, the reactions of the ylides with electron-deficient dipolarophiles can be attained without the direct reduction of dipolarophiles by the reductant. Less

Report

(4 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (44 results)

All Other

All Publications (44 results)

  • [Publications] A.Hosomi: "New Reactivity of Methoxyhydridosilane in the Catalytic Activation System"Tetrahedron Lett.. 40・5. 911-914 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Hosomi: "Highly Stereoselective Metathesis Reaction between Optically Active Hydrosilane and Copper(I) Salt in DMI"J. Organometal. Chem. 574・1. 102-106 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Hosomi: "Acid-Catalyzed Cyclization of Vinylsilanes Bearing an Amino Group. Stereoselective Synthesis of Pyrrolidines"Org. Lett. 2・3. 385-388 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Hosomi: "A Novel Catalytic System for the Mannich-type Reaction of Silyl Enolates : Stereoselective Synthesis of β-Aminoketone"Anger. Chem. 112・11. 2034-2036 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Hosomi: "Iron-Catalyzed Regio-and Stereoselective Carbolithiation of Alkynes"Angew. Chem. 113・3. 641-643 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Hosomi: "Lewis Acid-Catalyzed Reductive Amination of Carbonyl Compounds with Aminohydrosilanes"Synlett. 10. 1617-1619 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Hosomi: "Silicon(IV) Reagents"in Lewis Acid Reagents : A Practical Approach(The Practical Approach in Chemistry Series)"Oxford Science Publications. 351 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Makoto Hojo, Chikara Murakami, Atsuko Fujii, Akira Hosomi: "New Reactivity of Methoxyhydridosilane in the Catalytic Activation System"Tetrahedron Lett.. 40 (5). 911-914 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Hajime Ito, Tomoko Ishizuka, Tomoko Okumura, Hiroshi Yamanaka, Jun-ichi Tateiwa, Motohiro Sonoda, Akira Hosomi: "Highly Stereose?ective Metathesis Reaction between Optically Active Hydrosilane and Coppera) Salt in DMI"J. Organometal Chcm.. 574 (1). 102-106 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Hajime Ito, Tatsuki Yajima, Jun-ichi Tateiwa, Akira Hosomi: "An Unprecedented Catalytic Reaction Using Gold(I) Complexes"Tetrahedron Lett.. 40 (45). 7807-7810 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Katsukiyo Miura, Hiroshi Saito, Daisuke Itoh, Akira Hosomi: "Homolytic Allylation of Vinyl Iodides with Allylstannanes"Tetrahedron Lett.. 40 (50). 8841-8844 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Hajime Ito, Hiroshi Yamanaka, Tomoko Ishizuka, Jun-ichi Tateiwa, Akira Hosomi: "New Reactivity of a Reducing Reagent Generated from a Copper(I) Salt and a Hydrosilane : Selective Reduction of Ketones and Olefins Conjugated with an Aromatic Group"Synlett. (4). 479-482 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Hajime lto, Akira Hosomi: "New Synthetic Reactions Using Group 11 Metal Compounds as a Catalyst"J.Synth.Org.Chem.,Japan. 58 (4). 274-284 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Katsukiyo Miura, Kentaro Tamaki, Takahiro Nakagawa, Akira Hosomi: "A Novel Catalytic System for the Mannich-type Reaction of Silyl Enolates : Stereoselective Synthesis of β-Aminoketones"Angew. Chem., Int. Ed. Engl.. 39 (11). 1958-1960 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Hajime Ito, Hiroshi Yamanaka, Jun-ichi Tateiwa, Akira Hosomi: "Boration of an α, β-Enone using Diboron Promoted by a Copper(I)-Phosphine Mixture Catalyst"Tetrahedron Lett.. 41 (35). 6821-6825 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Katsukiyo Miura, Shigeo Okajima, Takeshi Hondo, Takahiro Nakagawa, Tatsuyuki Takahashi, Akira Hosomi: "Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hydroxy Group : A New Method for Stereoselective Synthesis of Disubstituted Tetrahydrofurans"J. Am. Owm. Soc.. 122 (46). 11348-11357 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Makoto Hojo, Yoshio Murakami, Hidenori Aihara, Rie Sakuragi, Yu Baba, Akira Hosomi: "Iron-Catalyzed Regio- and Stereoselective Carbolithiation of Alkynes"Angew. Chem. Int. Ed. Engl.. 40 (3). 621-623 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Makoto Hojo, Rie Sakuragi, Satoru Okabe, Akira Hosomi: "Allyl- and Propargylchromium Reagents Generated by a Chromiuman) Ate-type Reagent as a Reductant and their Reactions with Electrophiles"Chem. Commun.. (4). 357-358 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Katsukiyo Miura, Hiroshi Saito, Daisuke Itoh, Toshie Matsuda, Naoki Fujisawa, Di Wang, Akira Hosomi: "Allylstannylation of Carbon-Carbon and Carbon-Oxygen Unsaturated Bonds via a Radical Chain Process"J. Org. Chem.. 66 (10). 3348-3355 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Jun-ichi Tateiwa, Akira Hosomi: "Pentacoordinate Organosilicate-Catalyzed Michael Addition of p-Keto Ester to 3-Buten-2-one"European J. Org. Chem.. 4 (8). 1445-1448 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Katsukiyo Miura, Naoki Fujisawa, Hiroshi Saito, Di Wang, Akira Hosomi: "Synthetic Utility of Stannyl EnolateS as Radical Alkylating Agents"Org. Lett.. 3 (16). 2591-2594 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Katsukiyo Miura, Tatsuyuki Takahashi, Hisashi Nishikori, Akira Hosomi: "Acid-Catalyzed Cyclization ofVinylsilanes Bearing a Hemiacetal Group"Chem. Lett.. (10). 958-959 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Katsukiyo Miura, Kazunori Ootsuka, Shuntaro Suda, Hisashi Nishikori, Akira Hosomi: "Lewis AcidCatalyzed Reductive Amination of Carbonyl Compounds with Ammonydrosilanes"Synlett. (10). 1617-1619 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Makoto Hojo, Kyosuke Sakata, Nobuo Ushioda, Takeshi Watanabe, Hisashi Nishikon, Akira Hosomi: "Reductive Generation of Enolates Using Chromium(III) Ate-Type Reagent as a Reductant and Reactions of the Enolates with Electrophiles"Organometallics. 20 (24). 5014-5016 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A. Hosomi: "Iron-Catalyzed Regio- and Stereoselective Carbolithiation of Alkynes"Angew. Chem., Int. Ed. Engl. 40・3. 621-623 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A. Hosomi: "Allyl- and Propargylchromium Reagents Generated by a Chromium(III) Ate-type Reagent as a Reductant and their Reactions with Electrophiles"Chem. Commun.. 4. 357-358 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A. Hosomi: "Pentacoordinate Organosilicate-Catalyzed Michael Addition of b-Keto Ester to 3-Buten-2-one"European J. Org. Chem. 4・8. 1445-1448 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A. Hosomi: "Synthetic Utility of Stannyl Enolates as Radical Alkylating Agents"Org. Lett.. 3・16. 2591-2594 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A. Hosomi: "Lewis Acid-Catalyzed Reductive Amination of Carbonyl Compounds with Aminohydrosilanes"Synlett. 10. 1617-1619 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A. Hosomi: "Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hemiacetal Group"Chem. Lett.. 10. 958-959 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A.Hosomi: "Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hydroxy Group : A New Method for Stereoselective Synthesis of Disubstituted Tetrahydrofurans"J.Am.Chem.Soc.. 122・46. 11348-11357 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Hosomi: "New Reactivity of a Reducing Reagent Generated from a Copper(I) Salt and a Hydrosilane : Selective Reduction of Ketones and Olefins Conjugated with an Aromatic Group"Synlett. 4. 479-482 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Hosomi: "Acid-Catalyzed Cyclization of Vinylsilanes Bearing a Hydroxy Group.Benzyldimethylsilyl Group as an Effective Promoter and Novel Hydroxy Surrogate"Tetrahedron Lett.. 41・13. 2129-2132 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Hosomi: "A Novel Catalytic System for the Mannich-type Reaction of Silyl Enolates : Stereoselective Synthesis of β-Aminoketones"Angew.Chem.,Int.Ed.Engl.. 39・11. 1958-1960 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Hosomi: "First Gold Complex-Catalysed Selective Hydrosilylation of Organic Compounds"Chem.Commun.. 11. 981-982 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Hosomi: "Boration of an α,β-Enone Using a Diboron Promoted by a Copper(I)-Phosphine Mixture Catalyst"Tetrahedron Lett.. 41・35. 6821-6825 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Hosomi: "Non-Stabilized Carbonyl Ylides for α-Iodo Silyl Ethers : A Practical Approach (The Practical Approach in Chemistry Series)"Oxford Science Publications. 270 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Hosomi: "Reactivity of Rieke Manganese: Synthesis of Pyrrolidine and Piperidine Derivatives"Heterocycles. 49・1. 85-88 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Hosomi: "New Reactivity of Methoxyhydridosilane in the Catalytic Activation System"Tetrahedron Lett.. 40・5. 911-914 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Hosomi: "Highly Stereoselective Metathesis Reaction between Optically Active Hydrosilane and Copper(I) Salt in DMI"J.Organometal.Chem.. 574・1. 102-106 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Hosomi: "Hidroxy Group-Directed Homolytic Hydrostannylation of Alkenols with Dibutylchlorostannane"Chem.Lett.. 7. 659-660 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Hosomi: "An Unprecedented Catalytic Reaction Using Gold(I) Complexes"Tetrahedron Lett.. 40・45. 7807-7810 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Hosomi: "Homolytic Allylation of Vinyl Iodides with Allylstannanes"Tetrahedron Lett.. 40・50. 8841-8844 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A.Hosomi: ""Silicon (IV) Reagents" in Lewis Acid Reagents: A Practical Approach (The Practical Approach in Chemistry Series)."Oxford Science Publications. 270 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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