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1989 Fiscal Year Final Research Report Summary

New Method of Radical Formation and Its Application to Organic Synthesis

Research Project

Project/Area Number 63470074
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

UTIMOTO Kiitiro  Kyoto Univ., Fac. Eng., Professor, 工学部, 教授 (90025958)

Co-Investigator(Kenkyū-buntansha) MATSUBARA Seijiro  Kyoto Univ., Fac. Eng., Instructor, 工学部, 助手 (90190496)
OSHIMA Koichiro  Kyoto Univ., Fac. Eng., Assoc. Professor, 工学部, 助教授 (00111922)
Project Period (FY) 1988 – 1989
KeywordsRadical / Triethylborane / Triphenystannane / Addition / Cyclization / Triphenylgermane / Acetylene / Alkyl iodide
Research Abstract

Novel efficient method for the generation of organic radical species has been applied to organic syntheses. Triethylborane-initiated addition of triphenylstannane to acetylenes proceeds smoothly in high regio- and stereoselectivity. Application to an acetylene containing an olefinic bond at appropriate position provides a cyclized product stereoselectively; triphenyltin radical attacks at acetylene bond regioselectively to give a vinyl radical, which adds intramolecularly to an olefin stereoselectively. Triphenylgermane adds to a 1-alkyne under triethylborane catalysis. In this case, reaction is kinetically controlled at -78゚C to give Z-isomer, whereas reaction is thermodynamically controlled at 60゚C affording Enisomer predominantly. By the mechanistic investigation of the above reaction, an efficient procedure of the isomerization of olefin geometry has been devised. Alkyl halides can be reduced to the corresponding hydrocarbons by radical type reduction. Intramolecular addition of alkoxythiocarbonyl radical, an acyl radical equivalent, gives an -methylene lactone. Alkyl iodides add to acetylene smoothly under triethylborane catalysis to give vinyl iodides regio- and stereoselectively. Perfluoroalkyl iodides add to acetylenes analogously. Reaction of an -bromo ketone with a carbonyl compound in the presence of triethylborane gives a Reformatsky type reaction product; formation of boron enolate and reaction with aldehyde to give an aldol product. Triethylborane-mediated addition of an alkyl iodide to methyl vinyl ketone also gives a boron enolate. As the obtained boron enolate reacts with an aldehyde to give aldol product, the above reactions opens novel three components coupling reaction of alkyl iodide, methyl vinyl ketone, and aldehyde.

  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] 一瀬佳史: "Application of Free Radical Substitution Reaction into Interconversion of 1-Alkenylsulfides,1-Alkenylgermanes,and 1-Alkenylstannanes" Chemistry Letters. 669-672 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 一瀬佳史: "Et_3B-Induced Radical Reaction of 1,3-Diene Monoxide with C_6F_<13>I,PhSH, or Ph_3GeH" Chemistry Letters. 1437-1440 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 野崎京子: "Facile Routes to Boron Enolates.Et_3B-Mediated Reformatsky Type Reaction and Three Components Coupling Reaction of Alkyl Iodides,Methyl Vinyl Ketones and Carbonyl Compounds" Terahedron Letter. 29. 1041-1044 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 三浦勝清: "Triphenylstannyl Radical or Benzenethiyl Radical Promoted Transformation of 1,1-Dialkoxycarbonyl-2-(1,3-butadienyl)cyclopropanes into 2-Ethynyl-3-cyclopentenes" Tetrahedron Letters. 29. 1543-1546 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 一瀬佳史: "Hydrostannation and Hydrogermylation of Allenes" Bull.Chem.Soc.Jpn.61. 2693-2695 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 三浦勝清: "Synthesis of Vinylcyclopentanes from Vinylcyclopropanes and Alkenes Promoted by Benzenethiyl Radical" Tetrahedron Letters. 29. 5135-5138 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 野崎京子: "Facile Reduction of Dithiocarbonates with n-Bu_3SnH-ET_3B.Easy Access to Hydrocarbons from Secondary Alcohols" Tetrahedron Letters. 29. 6125-6126 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 野崎京子: "Synthesis of Lactones by Intramolecular Addition of Alkoxythiocarbonyl Free Radicals to Acetylenes" Tetrahedron Letters. 29. 6127-6128 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大嶌幸一郎: "新規ラジカル発生法とその有機合成への応用" 有機合成化学協会誌. 47. 40-52 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 三浦勝清: "Triethylborane-Induced Hydrodehalogenation of Organic Halides by Tin Hydrides" Bull.Chem.Soc.Jpn.62. 143-147 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 野崎京子: "Et_3B Induced Radical Addition of Ph_3SnH to Acetylenes and its Application to Cyclization Reaction" Tetrahedron. 45. 923-933 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 一瀬佳史: "Triethylborane-Induced Radical Addition of Alkyl Iodides to Acetylenes" Tetrahedron Letters. 30. 3155-3158 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 武山佳裕: "Triethylborane-Induced Stereoselective Radical Addition of Perffluoroalkyl Iodides to Acetylenes" Tetrahedron Letters. 30. 3159-3162 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 三浦勝清: "Stabilizing Effect of Trialkylsilyl Group on Carbon Radical:Radical Induced Ring Opening of 1-Trialkyl-Silyl-2-vinylcyclopropanes" Tetrahedron Letters. 30. 4413-4416 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] ICHINOSE, Yoshifumi: "Application of Free Radical Substitution Reaction into Interconversion of 1-Alkenylsulfides, 1-Alkenylgermanes, and 1-Alkenylstannanes" Chemistry Letters, 669-672, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] ICHINOSE, Yoshifumi: "Et_3B-Induced Radical Reaction of 1,3-Diene Monoxide with C_6F_<13>I, PhSH, or Ph_3GeH" Chemistry Letters, 1437-1440, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] NOZAKI, Kyoko: "Facile Routes to Boron Enolates. Et_3B-Mediated Reformatsky Type Reaction and Three Components Coupling Reaction of Alkyl Iodides, Methyl Vinyl Ketones and Carbonyl Compounds" Tetrahedron Letters, 29, 1041-1044, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] MIURA, Katsukiyo: "Triphenylstannyl Radical or Benzenethiyl Radical Promoted Transformation of 1, 1-Dialkoxycarbonyl-2-(1, 3-butadienyl)cyclo-propanes into 2-Ethynyl-3-cyclopentenes" Tetrahedron Letters, 29, 1543-1546, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] ICHINOSE, Yoshifumi: "Hydrostannation and Hydrogermylation of Allenes" Bull. Chem. Soc. Jpn. 61, 2693-2695, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] MIURA, Katsukiyo: "Synthesis of Vinylcyclopentanes from Vinylcyclopropanes and Alkenes Promoted by Benzenethiyl Radical" Tetrahedron Letters, 29, 5135-5138, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] NOZAKI, Kyoko: "Facile Reduction of Dithiocarbonates with n-Bu_3SnH-Et_3B. Easy Access to Hydrocarbons from Secondary Alcohols" Tetrahedron Letters, 29, 6125-6126, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] NOZAKI, Kyoko: "Synthesis of Lactones by Intramolecular Addition of Alkoxythiocarbonyl Free Radicals to Acetylenes" Tetrahedron Letters, 29, 6127-6128, 1988.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] OSHIMA, Koichiro: "New Method of Radical Formation. Radical Reactions with R_3SnH-Et_3B System" J. Syn. Org. Chem. Jpn., 47, 40-52, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] MIURA, Katsukiyo: "Triethylborane-Induced Hydrodehalogenation of Organic Halides by Tin Hydrides" Bull. Chem. Soc. Jpn. 62, 143-147, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] NOZAKI, Kyoko: "Et_3B Induced Radical Addition of Ph_3SnH to Acetylenes and its Application to Cyclization Reaction" Tetrahedron, 45, 923-933, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] ICHINOSE, Yoshifumi: "Triethylborane-Induced Radical Addition of Alkyl Iodides to Acetylenes" Tetrahedron Letters, 30, 3155-3158, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] TAKEYAMA, Yoshihiro: "Triethylborane-Induced Stereoselective Radical Addition of Perffluoroalkyl Iodides to Acetylenes" Tetrahedron Letters, 30, 3159-3162, 1989.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] MIURA, Katsukiyo: "Stabilizing Effect of Trialkylsilyl Group on Carbon Radical: Radical Induced Ring Opening of 1-Trialkylsilyl-2-vinylcyclo-propanes." Tetrahedron Letters, 30, 4413-4416, 1989.

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1993-03-26  

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