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Synthetic Studies on Adenine-Diterpene Alkaloids Asmarines A-F, Cytotoxic Metabolites from the Marine Sponge Raspailia Species

Research Project

Project/Area Number 12672051
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

OHBA Masashi  Kanazawa University, Center for Instrumental Analysis, Associate Professor, 機器分析センター, 助教授 (60115219)

Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2002: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2001: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2000: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsMarine sponge metabolite / Asmarine / Adenine / Clerodane diterpenoid / Hydroxylamine / Pyrimidine / Purine / Anti-cancer activity / プリン環 / シリエルエノールエーテル / 不斉Robinson環化 / アルキル化
Research Abstract

With a view to confirming the structures and absolute configurations of asmarines A-F, novel adenine-diterpene alkaloids, isolated from the marine sponge Raspailia sp., we have undertaken their chiral syntheses and obtained the following results.
1. Alkylation of 6-chloropurine with N-(3-bromopropyl)-N-(methoxymethoxy) carbamic acid allyl ester in the presence of Co-complex provided preferentially the 7-isomer, which was then converted to the hydroxylamine possessing a [1,4]diazepino[1,2,3-gh]purine skeleton corresponding to the heterocyclic portion of asmarines A,B via the intramolecular amination at the 6-position.
2. Separate alkylation of 6-chloro-7,9-dihydro-9-methyl-8H-purin-8-one at the 7-position with N-(3-bromopropyl)carbamic acid tert-butyl ester and with N-(3-bromopropyl)-N-methoxycarbamic acid tert-butyl ester and the subsequent cyclization at the 6-position afforded the amine and the methoxyamine corresponding to the heterocyclic moieties of asmarines C,D and asmarines E,F, respectively.
3. (4aR)-1,4a-Dimethyl-4,4a,7,8-tetrahydronaphthalene-2,5(3H, 6H)-dione , obtained by asymmetric Robinson annulation, was converted to (4'aR,5'S,6'R,8'aR)-octahydro-5',6',8'a-trimethylspiro[1,-dioxolane-2,1'(2'H)-naphthalene]-5'-carboxaldehyde having all stereogenic centers consistent with the trans-decalin skeleton of asrnarines A,D,E via highly stereoselective reactions (Li/NH_3 reduction, hydroxymethylation of the silyl enol ether, and catalytic hydrogenation using Ir catalyst).
Completion of two diterpene portions by side chain modification and subsequent introduction of the heterocyclic moieties are currently under way.

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (5 results)

All Other

All Publications (5 results)

  • [Publications] Masashi Ohba: "Adenine Diterpenoids"Res.Adv.in Organic Chem.. 1. 1-11 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masashi Ohba: "Preparatory Study for the Synthesis of the Marine Sponge Alkaloids Asmarines A-F : Synthesis of their Heterocyclic Portions"Heterocycles. 57. 1235-1238 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masashi Ohba: "Adenine Diterpenoids"Res. Adv. In Organic Chem.. 1. 1-11 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masashi Ohba and Takahiro Tashiro: "Preparatory Study for the Synthesis of the Marine Sponge Alkaloids Asmarines A-F : Synthesis of Their Heterocyclic Portions"Heterocycles. 57. 1235-1238 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masashi Ohba: "Preparatory Study for the Synthesis of the Marine Sponge Alkaloids Asmarines A-F : Synthesis of their Heterocyclic Portions"Heterocycles. 57・7. 1235-1238 (2002)

    • Related Report
      2002 Annual Research Report

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

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