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Development of useful lanthanide salt-induced cascade reactions and applications to natural products synthesis

Research Project

Project/Area Number 13672240
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionMEIJI PHARMACEUTICAL UNIVERSITY

Principal Investigator

NAGAOKA Hiroto  MEIJI PHARMACEUTICAL UNIVERSITY FACULTY OF PHARMACY PROFESSOR, 薬学部, 教授 (30155915)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2001: ¥2,100,000 (Direct Cost: ¥2,100,000)
KeywordsSamarium(II) iodide / cyclization / reductive coupling / gibberellins / 10-oxatricyclo[4.3.2.0^<1,5>] undecane-7, 11-diones / 11-oxatricyclo[5.3.2.0^<1,6>]undecane-8, 12-diones / spiro[4, 4]nonane / 10-oxatricyclo[4.3.2.0^<1.5>]undecane
Research Abstract

Much interest is presently being directed to reaction using lanthanide reagent in organic synthesis. Especially, samarium(II) iodide (SmI_2) has been effective in carbon-carbon bond forming reactions and considerable attention has been focused on various intramolecular processes. In the present investigation, we developed an effective SmI_2-induced cascade cyclization to form polycyclic compounds. Treatment of (2Z)-2-methyl-7-oxodec-2-ene-1, 10-dioic acid derivatives with SmI_2 in tetrahydrofuran caused cascade reductive cyclization-Dieckmann condensation-lactonization to give 6-methyl-10-oxatricyclo[4.3.2.0^<1,5>]undecane-7, 11-diones corresponding to A/B ring system of antheridiogen-An and gibberellins. And reaction of dimethyl (2Z)-2-methyl-8-oxoundec-2-ene-1, 10-dioate with SmI_2 gave 7-methyl-11-oxatricyclo[5.3.2.0^<1,6>]undecane-8, 12-diones corresponding to A/B ring system of resenolactone. A partial structure of ginkgolides, 7-oxatricyclo[6.3.0.0^<1,5>]undecan-6-one system, was also synthesized by similar method. An application of the cascade cyclization for the synthesis of gibberellins was then investigated. The construction of the C/D ring system involves two crucial steps : stereoselective photo cyclization of 2-cyclohexene derivative with allene to form 8-methylenebicyclo[4.2.0]octan-2-one system and SmI_2-induced pinacol coupling reaction. The SmI_2-induced cascade cyclization of the (2Z)-2-methyl-7-oxods-2-ene1, 10-dioate derivative bearing C/D ring system produced fully functionalized gibbane skeleton in good yield.
Thus the authors established an effective and direct one-step process for obtaining bicyclic ring systems with γ-lactone from simple acyclic compounds using one electron transfer reagent SmI_2. By these mild conditions, the use of strongly basic conditions for the Dieckmann condensation is avoided and good to excellent stereocontrol over newly formed ring junctures in the product is possible.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (9 results)

All Other

All Publications (9 results)

  • [Publications] Hiroaki Miyaoka: "Synthesis of the Optically Active Bicyclo[4.2.1]nonane Segment of Mediterraneols"Synlett. 2. 227-230 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Takehiko Yoshimitsu: "Synthesis of the CD Ring System of Paclitaxel by Atom-transfer Radical Annulation Reaction"Tetrahedron Letters. 43・47. 8587-8590 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Takehiko Yoshimitsu: "Hydroxyalkylation of α-C-H Bonds of Tetrahydrofuran with Aldehydes in the Presence of Triethylborane and tert-Butyl Hydroperoxide"The Journal of Organic Chemistry. 68・2. 625-627 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Hiroaki Miyaoka, Toshiyuki Yokokura, Takashi Okamura, Hiroto Nagaoka and Yasuji Yamada: "Synthesis of the Optically Active Bicyclo[4.2.1]nonane Segment of Mediterraneols"Synlett. 227-230 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Takehiko Yoshimitsu, Hideyuki Nakajima and Hiroto Nagaoka: "Synthesis of the CD Ring System of Paclitaxel by Atom-transfer Radical Annulation Reaction"Tetrahedron Letters. 43. 8587-8590 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Takehiko Yoshimitsu, Arano Y and Hiroto Nagaoka: "Hydroxyalkylation of a-C-H Bonds of Tetrahydrofuran with Aldehydes in the Presence of Triethylborane and tert-Butyl Hydroperoxide"J. Org. Chem.. 68. 625-627 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Hiroaki Miyaoka: "Synthesis of the Optically Active Bicyclo [4.2.1] nonase Segment of Mediterraneols"Synlett. 2. 227-230 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takehiko Yoshimitsu: "Synthesis of the CD Ring System of Paclitaxel by Atom-transfer Radical Annulation Reaction"Tetrahedron Letters. 43・47. 8587-8590 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Takehiko Yoshimitsu: "Hydroxyalkylation of α-C-H Bonds of Tetrahydrofuran with Aldehydes in the Presence of Triethylborane and tert-Buty Hydroperoxide"The Journal of Organic Chemistry. 68・2. 625-627 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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