• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Studies on Characteristic Reactions in the Chalcogeno -Baylis -Hillman Reactions

Research Project

Project/Area Number 12672056
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionGifu Pharmaceutical University

Principal Investigator

KATAOKA Tadashi  Gifu Pharmaceutical University, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (00082975)

Co-Investigator(Kenkyū-buntansha) WATANABE Shinichi  Gifu Pharmaceutical University, Faculty of Pharmaceutical Sciences, Research Assistant, 薬学部, 助手 (40275095)
IWAMURA Tatsunori  Gifu Pharmaceutical University, Faculty of Pharmaceutical Sciences, Lecturer, 薬学部, 講師 (70184900)
Project Period (FY) 2000 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2001: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2000: ¥2,200,000 (Direct Cost: ¥2,200,000)
KeywordsBaylis-Hillman reaction / sulfide / Lewis acid / Michael reaction / aldol reaction / halomethylene aldol / alkyne / β-haloacrylic acid ester
Research Abstract

In order to overcome the drawback of the Baylis-Hillman reaction, "the slow rate," we developed the chalcogemde-TiCl_4-mediated tandem Michael-aldol reactions. The reactions had been deemed to be a chalcogene version of the Baylis-Hillman reaction, because the Baylis-Hillman adducts were given after purification of the products by the preparative TLC on silica gel. However, the initial products were α-chloromethyl aldols and were dehydrochlorinated during purification by the preparative TLC. The reactions of S-ethyl thioacrylate and keto esters gave much better results than the Baylis-Hillman reactions of ten. The reactions of acetylenic ketones and esters produced α-chloromethylene aldols. The chalcogenides were necessary for the reactions of α,β-unsaturated esters. The reactions of acetylenic ketones and esters and α-keto esters did not occur when tertiary amines were used as a catalyst instead of a Chalcogenide and TiCl_4.
We next studied the reaction in which a chalcogenide worked as Lewis base and found that sulfanyl substituent intramolecularly added to an enone to form a cychc sulfomum betaine. The tandem Michael-aldol reactions of 1- [2-(methylsulfanyDphenyl]prop-2-en-1-one or the seleno congener with aldehydes in the presence of BF_3・E_2O gave the Baylis-Hillman adduct and onium salt, and 3-(α-hydroxybenzyl) selenochromanone from the seleno congener.

Report

(3 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] T.Iwamura, M.Fujita, T.Kawakita, S.Kinoshita, S.Watanabe, T.Kataoka: "Dimethyl Sulfide-boron tribromide-mediated Reactions of α,β-Unsaturated Ketones with Aldehydes : One-pot Synthesis of Baylis-Hillman Adducts and α-Halomethyl Enones"Tetrahedron. 57. 8455-8462 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Kataoka, H.Kinoshita, S.Kinoshita, T.Iwamura, S.Watanabe: "A Convenient Synthesis of α-Halomethylene Aldols or β-Halo-α-(hydroxyalkyl)-acrylates Using the Chalcogeno-Baylis-Hillman Reaction"Angew.Chem.Int.Ed.. 39. 2358-2360 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Kataoka, T.Iwama, H.Kinoshita, Y.Tsurukami, S.Tsujiyama, M.Fujita, E.Honda, T.Iwamura, S.Watanabe: "Chalcogenide-TiCL_4-mediated Reactions of S-Ethyl Thioacrylate with Aldehydes"J.Organomet.Chem.. 611. 455-462 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Kataoka, H.Kinoshita, T.Iwama, S.Tsujiyama, T.Iwamura, S.Watanabe, G.Muraoka, G.Tanabe: "Reexamination of Products and the Reaction Mechanism of the Chalcogeno-Baylis-Hilliman Reaction : Chalocogenide-TiCl_4-mediated Reactions of Electron-Deficient Alkenes with Aldehydes"Tetrahedron. 56. 4725-4731 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Kataoka, S.Kinoshita, H.Kinoshita, M.Fujita, T.Iwamura, S.Watanabe: "Self-assisted Tandem Michael-aldol Reactions Mechanism of α,β-Unsaturated Ketones with Aldehydes"Chemical Communications. 1958-1959 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kataoka, S. Kinoshita, H. Kinoshita, M. Fujita, T. Iwamura, S. Watanabe: "Selfassisted Tandem Michael-aldol Reactions Mechanism of α,β-Unsaturated Ketones with Aldehydes"Chem. Commun.. 1958-1959 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Iwamura, M. Fujita, T. Kawakita, S. Kinoshita, S. Watanabe, T. Kataoka: "Dimethyl Sulfide-boron tribromide-mediated Reactions of α,β-Unsaturated Ketones with Aldehydes : One-pot Synthesis of Baylis-Hillman Adducts and α-Halomethyl Enones"Tetrahedron. 57. 8455-8462 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kataoka, H. Kinoshita, S. Kinoshita, T. Iwamura, S. Watanabe: "A Convenient Synthesis of α-Halomethylene Aldols or (β-Halo-α-(hydroxyalkyl)acrylates Using the Chalcogeno-Baylis-Hillman Reaction"Angew. Chem. Int. Ed.. 39. 2358-2360 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kataoka, T. Iwama, H. Kinoshita, Y. Tsurukami, S. Fujiyama, M.Fujita, E. Honda, T. Iwamura, S. Watanabe: "Chalcogenide-TiCl_4 mediated Reactions of S-Ethyl Thioacrylate with Aldehydes"J. Organomet. Chem.. 611. 455-462 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Kataoka, H. Kinoshita, T. Iwama, S. Tsujiyama, T. Iwamura, S.Watanabe, O. Muraoka, G. Tanabe: "Reexamination of Products and the Reaction Mechanism of the Chalcogeno-Baylis-Hillman Reaction : Chalocogenide-TiCl_4-mediated Reactions of Electron-Deficient Alkenes with Aldehydes"Tetrahedron. 56. 5725-4731 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Kataoka, S.Kinoshita, H.Kinoshita, M.Fujita, T.Iwamura, S.Watanabe: "Self-assisted Tandem Michael-aldol Reactions Mechanism of α, β-Unsaturated Ketones with Aldehydes"Chemical Communications. 1958-1959 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Iwamura, M.Fujita, T.Kawakita, S.Kinoshita, S.Watanabe, T.Kataoka: "Dimethyl Sulfide-boron tribromide-mediated Reactions of α, β-Unsaturated Ketones with Aldehydes : One-pot Synthesis of Baylis-Hillman Adducts and α-Halomethyl Enones"Tetrahedron. 57. 8455-8462 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Kataoka,H.Kinoshita,T.Iwamura,S.Watanabe,G.Tanabe: "Reexamination of Products and the Reaction Mechanism of the Chalcogeno-Baylis-Hillman Reaction"Tetrahedron. 56. 4725-4731 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Kataoka,H.Kinoshita,S.Kinoshita,T.Iwamura,S.Watanabe: "A Convenient Synthesis of α-Halomethylene Aldols or β-Halo-α-(hydroxyalkyl) acrylates Using the Chalcogeno-Baylis-Hillman Reaction"Angew.Chem.Int.Ed.. 39. 2358-2360 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Kataoka,T.Iwama,H.Kinoshita,T.Iwamura,S.Watanabe: "Chalcogenide-TiCl_4-mediated Reactions of S-Ethyl Thioacrylate with Aldehydes"J.Organomet.Chem.. 611. 455-462 (2000)

    • Related Report
      2000 Annual Research Report

URL: 

Published: 2000-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi