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Generations of Organometallic Species by Novel Reduction Reactions and their Applieations to Organic Synthesis

Research Project

Project/Area Number 06650975
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionUniversity of Tsukuba

Principal Investigator

HOJO Makoto  Dept.of Chemistry, Univ.of Tsukuba, lecturer, 化学系, 講師 (50229150)

Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1994: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsAte-complex / Manganese / Silicon / Samarium / Carbonyl Ylid / カルボニルイリド / マンガン / ケイ素 / カルボニルイド / 金属-ハロゲン交換
Research Abstract

1. Copper ate-complexes serve as reductants and (E) -and (Z) -vinylcopper reagents can be prepared directly. (Chem.Lett.1994,437 ; Bull.Chem.Soc., Jpn.1994,67,1495.) Functionalized allylcopper reagents were also prepared selectively. (J.Chem.Soc., Chem.Commun.1994,2687.) Manganese ate-complexes react with alpha-holoketones to generate enolates of the parent ketones efficiently. Using these reactions, regioselectivities in alkylation and aldol reaction are controlled perfectly. (in preparation)
2. Reactivities of oxiranylallylsilanes, aminosilanes, thiomethylsilanes, and alkoxyhydrosilanes were investigated. (J.Organometal.Chem.1994,473, C1 ; Chem.Lett.1994,719 ; Heteroatom Chem.1994,5,229 ; Tetrahedron Lett.1995,36,571 ; Bull.Soc.Chim.Fr.1995,132,499.) (J.Organometal.Chem.1995,499,155.)
3. Novel methods for generation of non-stabilized carbonyl ylids were found. (J.Am.Chem.Soc.1996,118, in press ; Synlett, 1996, in press.)

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] M.Hojo,H.Harada,A.Hosomi: "A Novel and Efficient Generation of Functionalized Vinylcopper Reagents'and their Reactions with Electrophiles,Synthesis of β Methylthiobutenolides" Chem.Lett.437-440 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo,H.Harada,C.Watanabe,A.Hosomi: "Reductive Cupration of α-Cyanoketenedithioacelats,Generation of Functionalized (E)-Vinylcopper Reagents and their Reactions with Electrophiles" Bull.Chem,Soc.Jpn.67. 1495-1498 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo,H.Harada,C.Murakami,A.Hosomi: "Direct Generation and Reaotions of Solfur-Substituted Alylcopper Reagents by a Novel Reduction Reaction Using Organocuprute" J.Chem.Soc.,Chem.Commun.2687-2688 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo,N.Ishibashi,K.Ohsumi,K.Miura,A.Hosomi: "Reaction of 2-Oxiranylallylsilene with Acetals,Direct Introluction of a Vinyloxirane Moiety" J.Organometal.Chem.473. C1-C2 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo,M.Nagayoshi,A.Fujii,N.Ishibashi,T.Yamagi,K.Muura,A.Hosomi: "Introduction of Electrophiles to the α-Pusition of α、β-Unsaturated Aldehydes and Ketones by Sequential Conjugate Aminosilylation-Alkylation-Deamination" Chem.Lett.719-722 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo,N.Ishibashi,A.Hosomi: "Heteroarylthiomethylsilanes.Synthesis and Application to Heteroarylthiomethylation of Carbonyl Compounds" Heteroatom Chem. 5. 229-234 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Hajime Harada, and Akira Hosomi: "A Novel and Efficient Generation of Functionalized Vinylcopper Reagents and their Reactions with Electrophiles. Synthesis of beta-Methylthiobutenolides" Chem.Lett.3. 473-440 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Hajime Harada, Chika Watanabe, and Akira Hosomi: "Reductive Cupration of alpha-Cyanoketenedithioacetals. Generation of Functionalized (E) -Vinylcopper Reagents and their Reactions with Electrophiles" Bull.Chem.Soc.Jpn.67 (5). 1495-1498 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Naruyasu Ishibashi, Katsufumi Ohsumi, Katsukiyo Miura, and Akira Hosomi: "Reaction of 2-Oxiranylallylsilanes with Acetals. Direct Introduction of a Vinyloxirane Moiety" J.Organometal.Chem.473. C1-C2 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Masayuki Nagayoshi, Atsuko Fujii, Naruyasu Ishibashi, Toshiharu Yangagi, Katsukiyo Miura, and Akira Hosomi: "Introduction of Electrophiles to the alpha-Position of alpha, beta-Unsaturated Aldehydes and Ketones by Sequential Conjugate Aminosilylation-Alkylation-Deamination" Chem.Lett.4. 719-722 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Naruyasu Ishibashi, and Akira Hosomi: "Heteroarylthiomethylsilanes. Synthesis and Application to Heteroarylthiomethylation of Carbonyl Compounds" Heteroatom Chem.5 (3). 229-234 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Hajime Harada, Chikara Murakami, and Akira Hosomi: "Direct Generation and Reactions of Sulfur-Substituted Allylcopper Reagents by a Novel Reduction Reaction Using Organocuprate" J.Chem.Soc., Chem.Commun.23. 2687-2688 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Atsuko Fujii, Chikara Murakami, Hidekami, Hidenori Aihara, and Akira Hosomi: "Divergent Stereoselectivity in the Reduction of alpha, beta-Epoxy Ketones Using Hydridosilicates" Tetrahedron Lett.36 (4). 571-574 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Chikara Murakami, Hidenori Aihara, Ei-ichi Komori, Shinya Kohra, Yoshinori Tominaga, and Akira Hosomi: "Cross-Coupling Reaction of Pentacoordinate Alkenylsilicates with Organic Halides and Triflates Catalyzed by a Palladiium Complex" Bull.Soc.Chim.Fr.132. 499-508 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Chikara Murakami, Hidenori Aihara, Kyoji Tomita, Katsukiyo Miuura and Akira Hosomi: "Ene Preference in the Reaction of Allenylmethylsilanes with Heterodouble Bonds Mediated by a Lewis Acid" J.Organometal.Chem.499. 155-157 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Hidenori Aihara, and Akira Hosomi: "Unprecedented Reactions Mediated by Samarium : Approach to Non-Stabilized Carbonyl Ylids" J.Am.Chem.Soc.118 (in press). (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Makoto Hojo, Naruyasu Ishibashi, and Akira Hosomi: "Versatile Reactivities of Carbonyl Ylids toward Unactivated Alkenes and Heterodipolarophiles, and their Synthetic Use" Synlett. (in press). (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M. Hojo, A. Fujii, C. Murakami, H. Aihara, A. Hosomi: "Dirergent Stereoselectivity in the Reduction of α. β-Epoxy Ketones Using Hydridosilicates" Tetrahedron Lett.36. 571-574 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Hojo, C. Murakami, H. Aihara, E. Komori, S. Kahra Y. Tominaga, A. Hosomi: "Cross-Coupling Reaetion of Pentacordinate Alkenylsilicates with Organic Halides and Triflates Cataly2ed by a Palladium Complex" Bull. Soc. Chim. Fr.132. 499-508 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M. Hojo, C. Murakami, H. Aihara, K. Tomita, K. Miura, A. Hosomi: "Ene Preference in the Reaction of Allenylmethylsilanes with Hetero-clouble Bonds Mediated by a Lewrs Acid" J. Organometal. Chem.499. 155-157 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M. Hojo, H, Aihara A. Hosomi: "Jnprecedented Reactions Mediated by Samarium: Approach to Now-Stabili2ed Casbontl Ylids" J. Am. Chem. Soc.118(印刷中). (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] M. Hojo, N. Ishibashi, A. Hosomi: "Versatile Reactivities of Carbonyl Ylids toward Unactivated Alkenes and Heterodipolarophiles, and their Synthetic Use" Synlett. (印刷中). (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Hojo,H.Harada,A.Hosomi: "A Novel and Efficient Generation of Functionalized Vinylcopper Reagents and their Reactions with Electrophiles.Synthesis of β-Methylthiobutenolides" Chem.Lett.,. (3). 437-440 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Hojo,H.Harada,C.Watanabe,A.Hosomi: "Reductive Cupration of α-Cyanoketenedithioacetals.Generation of Functionalized (E)-Vinylcopper Reagents and their Reactions with Electrophiles" Bull.Chem.Soc.Jpn.67(5). 1495-1498 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Hojo,N.Ishibashi,K.Ohsumi,K.Miura,A.Hosomi: "Reaction of 2-Oxiranylallylsilanes with Acetals.Direct Introduction of a Vinyloxirane Moiety" J.Organometal.Chem.473. C1-C2 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Hojo,M.Nagayoshi,A.Fujii,N.Ishibashi,T.Yanagi,K.Miura,A.Hosomi: "Introduction of Electrophiles to the α-Position of α,β-Unsaturated Aldehydes and Ketones by Sequential Conjugate Aminosilylation-Alkylation-Deamination" Chem.Lett.(4). 719-722 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Hojo,N.Ishibashi,A.Hosomi: "Heteroarylthiomethylsilanes.Synthesis and Application to Heteroarylthiomethylation of Carbonyl Compounds" Heteroatom Chem.5(3). 229-234 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Hojo,H.Harada,C.Murakami,A.Hosomi: "Direct Generation and Reactions of Sulfur-Substituted Allylcopper Reagents by a Novel Reduction Reaction Using Organocuprate" J.Chem.Soc.,Chem.Commun.(23). 2687-2688 (1994)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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