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Synthesis of Highly Reactive Organometallic Compounds and its Application to Highly Selective Organic Synthesis

Research Project

Project/Area Number 06453131
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

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

Co-Investigator(Kenkyū-buntansha) MIURA Katsukiyo  University of Tsukuba, Chemistry, Assistant, 化学系, 助手 (20251035)
HOJO Makoto  University of Tsukuba, Chemistry, Lecturer, 化学系, 講師 (50229150)
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥7,400,000 (Direct Cost: ¥7,400,000)
Fiscal Year 1995: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1994: ¥5,800,000 (Direct Cost: ¥5,800,000)
Keywords1,3-Dipolar / 1,3-Elimination / Carbonyl ylids / Reductive metalation / Allylcopper / Samarium-mediated reactions / [3+2] Cycloaddition / Silicon-directed cyclization / 立体選択的合成 / 高選択的有機合成 / [3+2]環化付加 / フッ化セシウム / (シリルメチル)クロロメチルエーテル
Research Abstract

The following results are obtained in this research project.
1. Creation and Reactions of Carbonyl Ylides and Related 1,3-Dipolar Reagents
1,3-Dipolar reagents are important and interesting chemical species from both synthetic and theoretical points of view. The novel findings that simple carbonyl ylides, otherwise inaccessible, were indeed expediently generated by the silicon-based 1,3-elimination from alpha-aryl-substituted chloromethyl trimethylsilylmethyl ether under mild and neutral conditions which provided the powerful one-step synthesis of dihydrofurans and tetrahydrofurans and related heterocylesvia [3+2] cycloadditions to a variety of multiple pi-bonds including C=C,C=C,C=O,C=S,C=N,N=N.
2. Unprecedented Samarium-Mediated Reactions : Generation of Non-Stabilized Carbonyl Ylids
Samarium reveals a strong reducing ability and by virue of this character together with its oxophilicity, is widely applied to organic synthesis in the formation of carbon-carbon bonds and transformation of … More a variety of functionalities with high selectivities. In the course of our study on the generation and reactions of reactive species, we report herein the generation of novel active species, nonstabilized carbonyl ylids from iodomethyl silyl ethers mediated by samarium, otherwise inaccessible, and their [3+2] cycloadditions to a variety of unsaturated compounds such as aldehydes, alkenes, allenes, and alkynes.
3. Direct Generation and Reactions of Sulfur-Substituted Allylcopper Reagents by a Novel Reduction Reaction Using Organocuprate
Ketene dithioacetals bearing a chlorine atom at an allylic position are cleanly reduced to generate the corresponding allylcopper reagents by treatment with two equimolar amounts of dimethylcuprate derived from cuprous cyanide (Me_2Cu (CN) Li_2). This reaction displays remarkable contrast to hitherto known reactions of cuprates in a sense of highly chemoselective reduction (only metal-halogen exchange reaction occurs) toward substitution reactions and is formally a new type of reaction for the generation of allylcopper species.
4. Silicon-Directed Cyclization of Vinylsilanes Bearing Hydroxy Group Catalyzed by an Acid
The acid-catalyzed cyclization of vinylsilanes bearing a hydroxy group took place cleanly to give tetrahydrofurans and tetrahydropyans, and the addition of hydroxy group to vinylsilane proceeded in a syn stereoselective fashion. Less

Report

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

    (44 results)

All Other

All Publications (44 results)

  • [Publications] Akira HOSOMI: "Divergent stereogelectivity in the Reaction of α、β-Epoxy ketones Using Hydridosilicates" Tetrahedron Letters. 36(4). 571-574 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akira HOSOMI: "Silicon-Directed cyclization of Vinylsilane Bearing Hydroxy Group Catalyzed by an Acid" Tetrahedron Letters. 36(9). 1483-1486 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akira HOSOMI: "Cross-Coupling Reaction of Plutacoordinate Alkenylsilicates with Organic Halides and Triflates Catalyed by a Palladium Complex" Bull. Soc. Chin. France. 132. 499-508 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akira HOSOMI: "Ene Preference in the Reaction of Allemylmethylsilanes with Hetero-double Bonds Mediated by a Lewis acid" J. Organometal. Chem.499. 155-157 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akira HOSOMI: "Syutheses and Reactions of Synthetic Equivaleuts of New 1,3-Dipolar Reageuts Using N-Bis (methylthio) methylsne Derivatives" Chem. Pharm. Bull.43(9). 1425-1434 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akira HOSOMI: "Chemoselective Preparation of Ketones by the Grignard Reaction of N-Acylpyrazoles" J. Heterocyclic Chem.32. 25-27 (1995)

    • 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, and A.Hosomi: "A Novel and Efficient Generation of Functionalized Vinylcopper Reagents and their Reactions with Electrophiles. Synthesis of beta-Methylthiobutenolides" Chem.Lett.(3). 437-440 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo, H.Harada, and C.Watanabe, and A.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] C.Kashima, H.Harada, I.Kita, I.Fukuchi, and A.Hosomi: "The Preparation of N-Acylpyrazoles and their Behavior toward Alcohol" Synthesis. (1). 61-65 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] C.Kashima, K.Takabashi, and A.Hosomi: "Ozonolysis of Substituted Isoxazoles" Heterocycles. 37 (2). 1075-1082 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo, N.Ishibashi, K.Ohsumi, K.Miura, and A.Hosomi: "Reaction of 2-Oxiranylallylsilanes with Acetals. Direct Introduction of a Vinyloxirane Moiety" J.Organometal.Chem.473. C1-C3 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo, M.Nagayoshi, A.Fujii, N.Ishibashi, Y.Yanagi, K.Miura, and A.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] T.Nishio, Y.Mori, I.Iida, and A.Hosomi: "Photocycloaddition of Benzothiazole-2-thiones to Alkenes" Helv.Chim.Acta. 77 (4). 981-987 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] C.Kashima, I.Fukuchi, K.Takahashi, and A.Hosomi: "Aminolysis of N-Acylpyrazoles" Heterocycles. 38 (6). 1407-1412 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo, N.Ishibashi, and A.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] C.Kashima, I.Kita, K.Takahashi and A.Hosomi: "Chemoselective Preparation of Ketones by the Grignard Reaction of N-Acylpyrazoles" J.Heterocyclic Chem.(in press). (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo, H.Harada, C.Murakami and 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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Miura, D.Itoh, T.Hondo, and A.Hosomi: "Stereoselective Synthesis of Di-and Trisubstituted Alkenes via Intramolecular Addition of Vinyl Radicals to Alkenes" Tetrahedron Lett.35 (51). 9605-9608 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] C.Kashima, I.Fukuchi, and A.Hosomi: "Diatereoselective alpha-Alkylation of 2-Acyl-3-phenyl-1-menthopyrazoles" J.Org.Chem.59 (25). 7821-7824 (1994)

    • 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.Alhara, and A.Hosomi: "Diveregent 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] K.Miura, S.Okajima, T.Hondo, and A.Hosomi: "Silicon-Directed Cyclization of Vinylsilane Bearing Hydroxy Group Catalyzed by an Acid" Tetrahedron Lett.36 (9). 1483-1486 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo, C.Murakami, H.Aihara, E.Komori, S.Kohra, Y.Tominaga, and A.Hosomi: "Cross-Coupling Reaction of Pentacoordinate Alkenylsilicates with Organic Halides and Triflates Catalyzed by a Palladium Complex" Bull.Soc.Chim.Fr.132 (5-6). 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] C.Kashima, I.Kita, K.Takahashi, and A.Hosomi: "The Reformatsky Reaction of 1-Acyl-3,5-dimethylpyrazoles. A Convenient Preparation of 4-Amino-3-oxoalkanoic Acid Derivatives" J.Heterocyclic Chem.32 (3). 723-725 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Hojo, C.Murakami, H.Aihara, K.Tomita, K.Miura, and A.Hosomi: "Ene Preference in the Reaction of Allenylmethylsilanes with Hetero-double Bonds Mediated by a Lewis Acid" J.Organometal Chem.499 (1-2). 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] Y.Tominaga, K.Ogata, H.Ueda, S.Kohra, and A.Hosomi: "N-Bis (methylthio) methylene Derivatives.VII.Syntheses and Reactions of Synthetic Equivalents of New 1,3-Dipolar Reagents Using N-Bis (methylthio) methylene Derivatives" Chem.Pharm.Bull.43 (9). 1425-1434 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Akira HOSOMI: "Divergent Stereogelectivity in the Reaction of d, β-Epoxy Ketones Using Hydridosilicates" Tetrahedron Letters. 36(4). 571-574 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akira HOSOMI: "Silicon-Directed Cyelization of Vinylsilane Bearing Hydroxy Group Catalyzed by an Acid" Tetrahedron Letters. 36(9). 1483-1486 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akira HOSOMI: "Cross-Coupling Reaction of Peutacoordinate Alkeuyfsilicates with Organic Halides and Triflates Catalyed by a Palladium Complex" Bull. Soc. Chim. France. 132. 499-508 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akira HOSOMI: "Ene Proference in the Reaction of Allemylmethylsilanes with Hetero-double Bonds Mediated by a Leunis acid" J. Organometal. Chem.499. 155-157 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akira HOSOMI: "Syutheses and Reactions of Synthetic Equivaleuts of New 1,3-Dipolar Reagents Using N-Bis (methylthio) methylane Derivatives" Chem. Pharm. Bull.43(9). 1425-1434 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akira HOSOMI: "Chemoselective Preparation of Ketones by the Grignaral Reaction of N-Acylpyrazoles" J. Heterocychic Chem.32. 25-27 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Akira 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] Akira HOSOMI: "Reductive Cupration of α-Cyanoketenedithioacetals.Generation of Functionalized(E)-Vinylcopper Reagents and their Reactions with Electrophiles" Bull.Chem.Soc.Jpn.67. 1495-1498 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Reaction of 2-Oxiranylallylsilanes with Acetals.Direct Introduction of a Vinyloxirane Moiety" J.Organometal.Chem.473. C1-C3 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira 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] Akira HOSOMI: "The Preparation of N-Acylpyrazoles and their Behavior toward Alcohol" Synthesis. 1. 61-65 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Ozonolysis of Substituted Isoxazoles" Heterocycles. 37. 1075-1082 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Photocycloaddition of Benzothiazole-2-thiones to Alkenes" Helv.Chim.Acta. 77. 981-987 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Aminolysis of N-Acylpyrazoles" Heterocycles. 38. 1407-1412 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Heteroarylthiomethylsilanes.Synthesis and Application to Heteroarylthiomethylation of Carbonyl Compounds" Heteroatom Chem.5. 229-234 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Direct Generation and Reactions of Sulfur-Substituted Allylcopper Reagents by a Novel Reduction Reaction Using Organocuprate" J.Chem.Soc.,Chem.Commun.印刷中 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Stereoselective Synthesis of Di-and Trisubstituted Alkenes via Intramolecular Addition of Vinyl Radicals to Alkenes" Tetrahedron Lett.35. 9605-9608 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Divergent Stereoselectivity in the Reduction of α,β-Epoxy Ketones Using Hydridosilicates" Tetrahedron Lett.35(印刷中). (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Akira HOSOMI: "Encyclopedia of Reagents for Organic Synthesis." John Wiley & Sons,Ed.by L,A,Paguette, 1333 (1994)

    • Related Report
      1994 Annual Research Report

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

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