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Development of Synthetic Radical Reactions of Cyclic Compounds based on Characteristics of Silicon.

Research Project

Project/Area Number 06453135
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

OSHIMA Koichiro  Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (00111922)

Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥7,300,000 (Direct Cost: ¥7,300,000)
Fiscal Year 1995: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 1994: ¥4,500,000 (Direct Cost: ¥4,500,000)
KeywordsSilacyclobutane / Silacyclopentane / Radical Cyclization / Triethylborane / Tributyltin Hydride / Mixed Acetal / Aldol Reaction / α-ヨードアシルシラン / 2-ハロシラシクロペンタン / 7-エンド環化
Research Abstract

1.1-Allyloxy-2-bromo-1-phenylsilacyclopentane was synthesized by a ring-enlargement reaction of 1-allyloxy-1-phenylsilacyclobutane with LiCHBr_2. The treatment of 1-allyloxy-2-bromo-1-phenylsilacyclopentane with n-Bu_3SnH in the presence of a catalytic amount of Et_3B provided 2-oxa-1-silabicyclo [3.3.0] octane, which was converted into 1,3,6-triol by an oxidative cleavage of silicon-carbon bonds with H_2O_2. An intermolecular radical addition of 2-iodosilacyclopentane to acetylenic compounds afforded the corresponding iodoalkenes.
2.Treatment of ethyl benzoate or isopropyl formate with tert-butyldimethylsilyldibromomethyllithium gave alkyl silyl mixed acetal via 1,3-rearrangement of silyl group from carbon to oxygen. The reaction of the mixed acetals with allylsilane in the presence of Lewis acid afforded allylated ethers.
3.Treatment of 2-halo-2-trimethysilyloxirane with metal salts such as ZnCl_2, ZnBr_2, NaI,and AgBF_4 gave the corresponding alpha-haloacylsilanes in good yields. An addition of triethylborane to haloacylsilane provided boron enolate which reacted with aldehydes to give aldol type adducts with high stereoselectivity.

Report

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

    (10 results)

All Other

All Publications (10 results)

  • [Publications] Koichiro Oshima: "Triethylborane-induced radical cyclization of 1-allyloxy-2-halosilacyclopentane" Bull. Chem. Soc. Jpn.,. 68. 625-634 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichiro Oshima: "Preparation of alkyl silyl acetals from carboxylic esters with t-butyldimethylsilyl-dihalomethyllithium" Chemistry Lett.,. 461-462 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichiro Oshima: "Preparation of α-haloacylsilane and its use for triethylborane-induced Reformatsky type" Tetrahedron Lett.,. 36. 5353-5356 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichiro Oshima: "Triethylborane-Induced Radical Cyclization of 1-Allyloxy-2-halosilacyclopentane. Stereoselective Synthesis of 1,3,6-Triols Starting from Silacyclobutane" Bull.Chem.Soc.Jpn.68. 625-634 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichiro Oshima: "Preparation of Alkyl Silyl Acetals from Carboxylic Esters with tert-Butyldimethylsilyldihalomethyllithium. 1,3-Rearrangement of Silyl Group from Carbon to Oxygen" Chemistry Lett.461-462 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichiro Oshima: "Preparation of alpha-Haloacylsilane and its Use for Trienthylborane-Induced Reformatsky Type Reaction" Tetrahedron Lett.36. 5353-5356 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Koichiro Oshima: "Triethylborane-induced radical cyclization of 1-allyloxy-2-hrlosilacyclopentane" Bull. Chem. Soc. Jpn.68. 625-634 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Koichiro Oshima: "Preparation of alkyl silyl acetals from carboxylic esters with t-butyldimethylsilydihalomethyllithium" Chemistry Lett.,. 461-462 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Koichiro Oshima: "Preparation of α-haloacylsilane and its use for Triethylborane-induced Reformatsky type reaction" Tetrahedron Lett.,. 36. 5353-5356 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Koichiro Oshima: "Triethylborane-Induced Radical Cyclization of 1-Allyloxy-2-holosilacyilopentane.Stereoselective Synthesis of 1,3,6-Triols Starting from Silaayclobutane" Bull.Chem.Soc.Jpn.,. 68. 625-634 (1995)

    • Related Report
      1994 Annual Research Report

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

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