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STUDIES ON NOVEL ORGANIC REACTION AND STEREO-REGULATION USING SILICON-, TIN-, AND RELATED ELEMENT COMPOUNDS

Research Project

Project/Area Number 03453025
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionUNIVERSITY OF TSUKUBA

Principal Investigator

HOSOMI Akira  U. OF Tsukuba, Chemistry, Professor, 化学系, 教授 (00004440)

Co-Investigator(Kenkyū-buntansha) HOJO Makoto  U. OF Tsukuba, RESEARCH ASSOCIATE, 化学系, 助手 (50229150)
KASHIMA Choji  U. OF Tsukuba, ASSOCIATE PROFESSOR, 化学系, 助教授 (60015568)
Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥8,100,000 (Direct Cost: ¥8,100,000)
Fiscal Year 1992: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 1991: ¥6,400,000 (Direct Cost: ¥6,400,000)
Keywords1,3-Dipolar Reagent / Azomethine Ylide / Organometallic Compound / Organosilicon Compound / [3+2]Cycloaddition / Unstable Chemical Species / Titanium Amide / Tandem Conjugate Addition / 有機スズ化合物 / 1,3-双極子 / 複合糸反応剤 / 高選択的合成 / アゾメチンイリド / 反応性有機ケイ素化合物 / 合成等価体 / 有機合成 / 不斉還元 / 高配位ケイ素化合物 / 1,3ー双極子試薬
Research Abstract

1. Highly Selective Allylation Using Pentacoordinate Organosilicates On of the most interesting features in organosilicon chemistry is that stable high coordinate species can be isolated. We have found that pentacoordinate allylsilicates and related compounds, unknown hitherto, can be readily prepared and used as nucleophiles, some of which are reported. Topics are preparation of pentacoordinate allylsilicates, substituted by alkoxy groups,which are useful and storable reagents, regio- chemo- and stereoselective allylations of carbonyl compounds without catalyst, and stereochemical outcomes of asymmetric allylation with optically active allylsilicates which are interpreted by a six-membered cyclic transition state, in sharp contrast with an anti-SE^1 mechanism for the allylation using tetracoordinate allylsilane.
2 Novel Synthesis of Alkylideneazomethine Yilds and Related 1,3-Dipolar Reagents and Synthetic Application to Organic Synthesis^2 Azomethine ylids and related 1,3-dipolar reagents are important and interesting chemical species from both synthetic and theoretical points of view. These species are generally unstable and inaccessible if the dipolar centers are not stabilized by electron-withdrawing or conjugating groups. We report here that a variety of N-silylmethyl-substituted ketene N,S-acetals react smoothly with activated alkenes, carbonyl compounds, and thioketones in the presence of cesium fluoride, to afford alpha-alkylidenepyrrolidines, oxazolidines, and thiazolidines, via a 1,3-elimination of methylthiotrimethylsilane. Similarly, N-silylmethyl- substituted isothioureas react with carbonyl and thiocarbonyl compounds promoted by fluoride ion to give the corresponding [3 + 2] cycloadduct, 2-imino-1,3-oxazolidines and 2-imino-1,3-thiazolidines in good yield. These reagents can be viewed as synthetic equivalents of alkylideneazomethine ylids and iminoazomethine ylids.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (45 results)

All Other

All Publications (45 results)

  • [Publications] A.Hosomi: "New Synthesisand Diels-Alder Reactions of 2-Aminomettiyl-1,3-butadieue and Related 1,3-Dienes" Bulletin of Chem.Soc.Jaapan. 64. 1051-1053 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi: "Tandem Conjugate Addition-Aldol Reactions of α,β-Unsaturated.Esters and Ketones" Tetrahedron Letters. 32. 2371-2374 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi: "Methylthoomethylation of Carbonyl Compounds Using Bis-(trimettiyl silylmettiyl)Sultide Promoted by Flouride Ion" Synpett. 3. 557-558 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Tominaga: "Synttiesisand(3+2)Cycloaddition of N-(Trimethyl silylmethyl)isothioureas:A Synthetic Equiualent of Novel 1,3-Dipolar Reagent,Iminoazowethine Yeide" Tetrahedron Letters. 32. 5987-5990 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Tominaga: "New Synthesis of Thiiranes by Fluoride Eou-Promoted Reaction of S-Mettiyl-S-trimethylsilylmenthyl N-(p-Toluenesulfonyl)dithioiminocarbonate and 2-(Jrimettiylmethylthio)thiazoline with Sldehydes" Tetrahedron Letters. 33. 85-88 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi: "Syuthesis of Organozilicon Compounds as Sythetic Equiralents of Unstable Active Chenical Species and their Applications to Highly Selective Syutheses of Heterocycles" J.Shyth.Org.Chem.,Japan. 50. 48-60 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi: "Organic Synthesis Utilizing Chanectenictics of Organosilicon Componds" J.Pharnaceutical Soc.,Japan. 112. 147-160 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] C.KAshima: "Ozonolysis of 1-Substituted Jnidazoles" Heterocyeles. 33. 385-390 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Aoyama: "Photocychization of 4-(Diolkylawino)-2-arlyl-1-buteues" J.Orgamic Chewistiy. 57. 3037-3041 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Hojo: "Alkoxymethylthiomethylsilanes as a Synthetic Equiralent of Thioearbonyl Ylidel.Sipithesis of 1,3-Oxathiolanes and Tetrabycrathiophenes" Chemistry Letters. 1073-1076 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Hojo: "Synthesis and Reactions of 2-Cyclopropyl-2-propenylsilaues.Silcon-Directed Generation of Cyclopropylcsrbiryl System" Tetrahedrou Letters. 33. 5981-5982 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi: "Structure and Reactirities of Peutacoordinate Organosilicon Cowpounds.Application of Highlysielective Organic Syuthesis" Reuieuis on Heteroatom Chemistry. 7. 214-228 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 細見 彰: "続医薬品の開発第35巻合成医薬品(V)合成反応剤" 広川書店, 336 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi: "Comprehensive Orgamic Synthesis" Plrgamon, 1333 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] 細見 彰: "合成化学者のための実験有機金属化学" 講談社サイエンティフィック, 270 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi, T.Masunari, Y.Tominaga, and M.Hojo: "New Synthesis and Diels-Alder Reactions of 2-Aminomethyl-1,3-butadienes and Related 1,3-Dienes" Bull. Chem. Soc. Japan. 64(3). 1051-1053 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi, T.Yanagi, and M.Hojo: "Tandem Conjugate Addition-Aldol Reactions of alpha,beta-Unsaturated Esters and Ketones" Tetrahedron Lett.32(21). 2371-2374 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi, K.Ogata, M.Ohkuma, and M.Hojo: "Methylthiomethyation of Carbonyl Compounds Using Bis(trimethylsilylmethyl) Sulfide Promoted by Fluoride Ion" Synlett. 3(8). 557-558 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Tominaga, K.Ogata, S.Kohra, M.Hojo, and A.Hosomi: "Synthesis and [3+2]Cycloaddition of N-(Trimethylsilylmethyl)isothioureas: A Synthetic Equivalent of Novel 1,3-Dipolar Reagent, Iminoazomethine Ylide" Tetrahedron Lett.32(42). 5987-5990 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Tominaga, H.Ueda, K.Ogata, S.Kohra, M.Hojo, M.Ohkuma, K.Tomita, and A.Hosomi: "New Synthesis of Thiiranes by Fluoride Ion-Promoted Reaction of S-Methyl-S'-trimethylsilyl- methyl N-(p-Toluenesulfonyl)dithioiminocarbonate and 2-(Trimethylsilylmethylthio)thiazoline with Aldehydes" Tetrahedron Lett.33(1). 85-88 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Tominaga, M.Hojo, and A.Hosomi: "Synthesis of Organosilicon Compounds as Synthetic Equivalents of Unstable Active Chemical Species and their Applications to Highly Selective Synthesis of Heterocylcles" J. Synth. Org. Chem., Japan. 50(1). 48-60 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi and M.Hojo: "Organic Synthesis Utilizing Characteristics of Organosilicon Compounds" J. Pharmaceutical Soc. Japan. 112(3). 147-160 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] C.Kashima, K.Harada, and A.Hosomi: "Ozonolysis of 1-Substituted Imidazoles" Heterocycles. 33(1). 385-390 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] H.Aoyama, J.Sugiyama, M.Yoshida, H.Hatori, and A.Hosomi: "Photocyclization of 4-(Dialkylamino)-2-aryl-1-butenes" J. Org. Chem.57(11). 3037-3041 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Hojo, M.Ohkuma, and A.Hosomi: "Alkoxymethylthiomethylsilanes as a Synthetic Equivalent of Thiocarbonyl Ylides. Synthesis of 1,3-Oxathiolanes and Tetrahydrothiophenes" Chem Lett.1073-1076. (6) (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] M.Hojo, K.Ohsumi, and A.Hosomi: "Synthesis and Reactions of 2-Cyclopropyl-2-propenylsilane. Silicon-Directed Generation of Cyclopropylcarbinyl System" Tetrahedron Lett.33(40). 5981-5982 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi: "Structure and Reactivities of Pentacoordinate Organosilicon Compounds. Application to Highly Selective Organic Synthesis" Reviews on Heteroatom Chemistry.7. 214-228 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Akira Hosomi: Hirokawa Book, Co.Development of Drugs Vol.35, Synthetic Drugs (V): Synthetic Reagents, 336 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Akira Hosomi: Permagon. Comprehensive Organic Synthesis, 1333 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Akira Hosomi: Kodan-sha Scientific. Experimental Organometallic Chemsitry for Synthetic Organic Chemsits, 270 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] A.Hosomi: "Organic Synthesis is Utilizing Characteic ticsoj Organosilicon Compounds" Jipharmaceutical Soc.Japan.112. 147-160 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] C.Kashima: "OZonolysis of 1-Sabstituted Imidazoles" Heterocyeles. 33. 385-390 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Aoyama: "Photocyclization of 4-(Dialkylauino)-2-aryl-1-buteues" J.Orgamic Chernistry. 57. 3037-3041 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Hojo: "Alkoxymethylttio Mettyl Silanes as aSy nthetic Equivakit of Thio-carbonyl Ylides.Syuthesis of 1,3-Oxathiolanes andTe tralyds of thiophenes" Chemistry Letters. 1073-1076 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] M.Hojo: "Synthesis and Reactions of 2-Cyclopropyl-2-Propenylsilaues.Silicon-Diyected Generation of Cyclopropylcasl inyl Systen" Tetoahedron Letters. 33. 5981-5982 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] A.Hosomi: "Structure and Reactirities of Reutacoordinate Orgauosilicon Conpowrds.Application to Highly Selective Organic Syutlesis" Revieus on Heteroatom Chemisty. 7. 214-228 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] 細見 彰: "合成化学者のための実験有機金属化学" 講談社サイエンティフィック, 270 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] A,Hosomi: "New Synthesis and DielsーAlder Reacflons of 2 Aminomethylー1,3ーbutaplienes and Related 1,3ーDienes" Bull,Chem.Soc.Japan. 64. 1051-1053 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] A.Hosomi: "Tandem Conjugate AdditionーAldol of d,βーUnsaturated Esters and Ketones" Terahedron letters. 32. 2371-2374 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] A・Hosomi: "Methylthiomethylation of Carbonyl Compounds Using Bischrinethylsilyl Sulfids Promoted by Fluoride Ion" Synlett. 3. 557-558 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] A.Hosomi: "Synthesis and[3+2]Cycloaddifion of Nー(trimethylsilylmethyl) isothioureas:Aspithetic Eguiralent of Novel 1,3ーDipdar Reagent Iminoazomethine Ylide" Telrahedron Letters. 32. 5995-5998 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] A.Hosomi: "New Synthesis by Fluoride IonーPromoted Reaction of SーMethylーSーtrimethylsilylmethyl Nー(Pーtoluenesugonf)dithioimlino carbonate and 2ー(trimethyl silymethylthio)thiazaline with Aldenydes" Tetrahedren Letters. 33. 85-88 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] A.Hosomi: "Synthesis of organosilicon Conpounds as Synthetic Eguivalents of Unstalle Active Chemical Species and their Applications to Highly Seletive Synthesis of Heteso eycles" J.Synth.Org.Chem.Japan. 50. 48-60 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] 細見 彰: "続医薬品の開発第35巻「合成医薬品(V)合成反応剤」" 広川書店, 336 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 細見 彰: "実験化学講座25「有機合成VII,有機全属試薬による合成」" 日本化学会.(丸善), 506 (1991)

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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