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Studies on the development of new, practical synthetic methods for the synthesis of physiologically active compounds related to vitamin D

Research Project

Project/Area Number 06555281
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section試験
Research Field Synthetic chemistry
Research InstitutionOkayama University

Principal Investigator

SAITO Seiki  Okayama University, Faculty of Engineering, Professor, 工学部, 教授 (60033239)

Co-Investigator(Kenkyū-buntansha) NITTA Issei  Fuji Pharmaceutical Industry, Research Manager, 研究部長
MANDAI Tadakatsu  Kurashiki University of Science and the Arts, College of Science and Industrial, 大学産業技術学部, 教授 (80131621)
ISHIKAWA Teruhiko  Okayama University, Faculty of Engineering, Instructor, 工学部, 助手 (10263617)
Project Period (FY) 1994 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥6,500,000)
Fiscal Year 1996: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1995: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1994: ¥4,000,000 (Direct Cost: ¥4,000,000)
KeywordsVitamin D / A-Ring asym, syn. / alpha-Silyl allyl anion / Peterson olefination / Intram.nitril oxide cycloadd. / C,D-Ring asym.syn. / Asym.intram.W.-E.Reac. / 不斉合成 / 分子内[3+2]環化付加 / ニトリルオキシド / ジアステレオ選択的 / ビタミンD誘導体A環単位 / アセタール開裂 / BnO-TBSO-グリセルアルデヒド / 選択的還元 / 活性型ビタミンD製剤 / Wadsworth-Emmons反応 / ジアステレオ場選択 / 分子内縮合 / 新光学活性合成単位 / 収束的全合成 / フェニルメンチル基
Research Abstract

The subject of this research is to establish versatile methods for the synthesis of Vitamin D and related compounds which can be submitted to physiological tests to systematically investigate the structure-activity relationship. The research takes advantage of convergent strategy and covers following categories : the development of novel methods for the asymmetric synthesis of C,D- and A-rings, which can be coupled by unprecedented methodology featuring nature-friendly and short-cut processes. The C,D-ring synthon has been prepared in 98.3 %de based on diastereoselective intramolecular Wadsworth-Emmons reaction relying on phenylmenthyl group as a chiral auxiliary. The optically pure A-ring synthon has been in hand efficiently by means of intramolecular 1,3-dipolar cycloaddition reaction of optically pure omega-olefinic dihydroxylnitriloxide which can be derived conveniently from optically pure ethyl (3S) -3,4-dihydroxybutanoate derivative available in multigram quantities from natural L-malic acid. Also, though remained at the stage of model reaction, it has been shown that Peterson-type olefination reaction between alpha, beta-unsaturated aldehyde and allylsilane may be promising for the forthcoming coupling process of the A-ring synthon with C,D-ring synthon. The methods developed in this research seem applicable to the synthesis of structurally diversed vitamin D derivatives. We will get involved in this research for the time being whcih would hopefully make the methods much better in terms of synthetic steps involved or availability of starting chiral templates for the C,D-ring synthon.

Report

(4 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] T.Mandai,Y.Tsujiguchi,S.Matsuoka,J.Tsuji,and S.Saito: "Preparation of Triesters by Palladium-Catalyzed Vicinal Carbonylation of 1-Substituted-3-methoxycarbonyl-2-propye Methyl Carbonates" Tetrahedron Lett.,. 35. 5697-5700 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Mandai,Y.Tsujiguchi,J.Tsuji,and S.Saito: "Tandem Pd-Catalgzed Carbonylation and Intramolecular Ene Reaction of 1-(2-Methoxycarbonylethynyl)-4-alkenyl Methyl Carbonates" Tetrahedron Lett.,. 35. 5701-5704 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Mandai,Y.Tsujiguchi.S.Matsuoka,S.Saito,J.Tsuji: "ANew Candidate for a Properly Substituted CD Ring Componenent of Vitamin D_3 via Intramolecular Asymmetric Olefination of a 1,3-Cyclopentanedione Derivative" J.Org.Chem.59. 5847 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Mandai,Y.Tsujiguchi,S.Matsuoka,S.Saito,J.Tsuji: "Preparation of α-Vinylidene-γ-lactones by Pd-catalyzed Carbonylation of 5-Hydroxy-2-alkyny Methyl Carbonates under Mild Conditions" J.Organometal.Chem.488. 127-131 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Seiki Saito,Akiyoshi Kuroda,Kazuya Tanaka,and Ryoichi Kimura: "A Novel Reducing System for Acetal Cleavage : BH_3・S(CH_5)_2-BF_3・S(C_2H_3)_2Combination" Synlett,. 231-233 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Seiki Saito,Akiyoshi Kuroda,Hiroshi Matsunaga,Shushiro Ikeda: "Synthesis of Chiral 3E 5E-Octadiene-1,2R,7R,8-Tetraol Frameworks by Means of Palladium(II)-Promoted Hetero-Claisen Rearrangement : Mechanistic Aspect" Tetrahedron,. 52. 13919 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Preparation of Triesters by Palladium-Catalyzed Vicinal Carbonylation of 1-Substituted-3-methoxycarbonyl-2-propyl Methyl Carbonates: "T.Mandai, Y.Tsujiguchi, S.Matsuoka, J.Tsuji, and S.Saito" Tetrahedron Lett.35. 5697-5700 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Tandem Pd-Catalyzed Carbonylation and Intramolecular Ene Reaction of 1- (2-Methoxycarbonylethynyl) -4-alkenyl Methyl Carbonates: "T.Mandai, Y.Tsujiguchi, J.Tsuji, and S.Saito" Tetrahedron Lett.35. 5701-5704 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A New Candiadate for a Properly Substituted CD Ring Component of Vitamin D_3 via Intramolecular Asymmetric Olefination of a 1,3-Cyclopentanedione Derivative: "T.Mandai, Y.Tsujiguchi, S.Matsuoka, S.Saito, J.Tsuji" J.Org.Chem.59. 5847 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Preparation of alpha-Vinylidene-gamma-lactones by Pd-catalyzed Carbonylation of 5-Hydroxy-2-alkynyl Methyl Carbonates under Mild Conditions: "T.Mandai, Y.Tsujiguchi, S.Matsuoka, S.Saito, J.Tsuji" J.Organometal.Chem.488. 127-131 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A Novel Reducing System for Acetal Cleavage : BH_3・S (CH_3) _2-BF_3・O (C_2H_5) _2 Combination: "Seiki Saito, Akiyoshi Kuroda, Kazuya Tanaka, and Ryoichi Kimura" Synlett. 231-233 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Synthesis of Chiral 3E,5E-Octadiene-1,2R,7R,8-Tetraol Frameworks by Means of Palladium (II) -Promoted Hetero-Claisen Rearrangement : Mechanistic Aspect: "Seiki Saito, Akiyoshi Kuroda, Hiroshi Matsunaga, Shushiro Ikeda" Tetrahedron. 52. 13919 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Teruhiko Ishikawa: "Synthesis and Asmmetric [3+2] Cycloaddition Reactions of Chiral Cyclic Nitrone : A Novel System Providing Maximal Facial Bias for both Nitrone and Dipolarophile" Angewandte Chemie International Edition in English. 35・16. 1863-1864 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Tadakatu Mandai Yuichi Kaihara Jiro Tsuji: "A New Candidate for a Properly Substituted CD Ring Component of Vitamin D_3 via Intramolecular Asymmetric Olefination of a 1,3-Cyclopentanedione Derivative" The Journal of Organic Chemistry. 59. 5847-5849 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Mandai,Y.Tsujiguchi,S.Matsuoka,J.Tsuji,S.Saito: "Preparation of Triester by Palladium-Catalyzed Vicinal Carbonylation of 1-Substituted-3-methoxycarbonyl-2-propynyl Methyl Carbonates" Tetrahedron Letters. 35. 5697-5700 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Mandai,Y.Tsujiguchi,J.Tsuji,S.Saito: "Tandem Pd-Catalyzed Carbonylation and Intramolecular Ene Reaction of 1-(2-Methoxycarbonyl-ethynyl)-4-alkenyl Methyl Carbonates" Tetrahedron Letters. 35. 5701-5704 (1994)

    • Related Report
      1994 Annual Research Report

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

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