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ジェンアセタールを利用する生物活性化合物の実用的合成

Research Project

Project/Area Number 18032043
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOsaka University

Principal Investigator

藤岡 弘道  Osaka University, 薬学研究科, 准教授 (10173410)

Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 2007: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2006: ¥3,100,000 (Direct Cost: ¥3,100,000)
Keywordsキラルアセタール / ジエンケタール / 分子内ハロエーテル化反応 / ドミノ反応 / オキソニウムイオン中間体 / 不斉合成 / スピロケタール / 光学活性ジオール / シクロヘキサジエンアセタール / (+)-Sch 642305 / ラジカル還元 / マクロラクトン化 / 10員環マクロライド / Chiral Auxiliary Multi-Use Methodology
Research Abstract

研究課題であるジエンアセタールを利用する生物活性化合物の実用的合成に関連して、鎖状ジエンケタールに対する分子内ハロエーテル化反応とその利用について検討し、以下の成果を得た。(1)C2対称性光学活性ヒドロベンゾインを不斉源とした鎖状ジエンケタールのドミノ型分子内ハロエーテル化反応を開発した。(2)光学補助剤由来のヒドロキシエチルユニットをcerium ammonium nitrate(CAN)を用いて除去することに成功した。さらに、ヒドロキシエチルユニットはヒドロベンゾイン由来のものに限定されないことも見出した。(3)2)の除去法が2-ヒドロキシエチルアミンにも適用できることを明らかにし、収率よく、アミノ化合物を得ることに成功した。(4)不斉補助基を除去することにより、収率良く[5.5]及び[5.6]スピロケタール構造を構築することに成功した。また分子内ハロエーテル化反応の立体化学を明らかにした。(5)C2対称性光学活性ヒドロベンゾインでなく、非対称の光学活性1-フェニル-1,3-プロパンジオールを不斉補助基とした鎖状ジエンケタールに対する分子内ハロエーテル化反応が立体選択的に進行することを明らかにした。またその不斉補助基を効率よく除去し、スピロケタール構造を構築することに成功した。また分子内ハロエーテル化反応の立体化学を明らかにした。(6)胃がんの原因菌であるピロリ菌に有効なスピロラキシンのスピロケタール部分構築の足がかりを得た。(7)ウンデカ-1,10-ジエン-6-オンモノアセタールの分子内ハロエーテル化反応はヒドロベンゾイン由来の5員環アセタールでは進行しないが、ジエン部が対称である事に着目し、光学活性ジオールとして入手容易な非対称な1-フェニル-1,3-プロパンジオール由来の6員環アセタールを用い、立体選択的ドミノ型分子内ハロエーテル化反応を起こさせる事に成功した。

Report

(2 results)
  • 2007 Annual Research Report
  • 2006 Annual Research Report
  • Research Products

    (39 results)

All 2008 2007 2006

All Journal Article (20 results) (of which Peer Reviewed: 11 results) Presentation (17 results) Book (2 results)

  • [Journal Article] A New Chiral Hypervalent Iodine(III) Reagent for Enantioselective Desymmerization of Phenols : A Profile of the Associative Pathway2008

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Angew. Chem. Int. Ed. 47

      Pages: 3787-3790

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Facile formation of tetrahydrofurans with multiple chiral centers using double iodoetherification of s-symmetric diene acetals : short asymmetric total synthesis of rubrenolide and rubrynolide2008

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Tetrahedron 64

      Pages: 4233-4245

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] ALKYL-AND ARYLATION OF OXACYCLIC ETHERS WITH TRIMETHYLSILYL TRIFRATE-2,4,6-COLLIDINE-GILMAN REAGENT COMBINATION : REMARLKA- BLE DISCRIMINATION OF TWO ETER OXYGEN2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Heterocycles 72

      Pages: 529-540

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Facile and Efficient Synthesis of Lactols by Domino Reaction of 2,3-Epoxy Alcohols Using Hypervalent Iodine(III) Reagent and Its Application to the Synthesis of Lactones and Asymmetric Synthesis of (+)-Tanikolide2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Chem. Eur. J. 13

      Pages: 5238-5248

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] New Three Component Reaction : Novel Formation of Seven-Membered Ring by the Unexpected Reaction at the γ-Position of the β-Keto Ester2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Org. Lett. 9

      Pages: 1687-1690

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Organic Chemistry Using Weakly Electrophilic Salts : Efficient Formation of O,O-Mixed, O,S- and N,O-Acetals2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      J. Org. Chem. 72

      Pages: 7898-7902

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Concise Asymmetric Total Synthesis of Scyphostatin, a Potent Inhibitor of Neutral Sphingomyelinase2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Chem. Eur. J 13

      Pages: 10225-10238

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Facile and Efficient Synthesis of Lactols by Domino Reaction of 2,3-Epoxy Alcohols Using Hypervalent Iodine(III) Reagent and Its Application to the Synthesis of Lactones and Asymmetric Synthesis of (+)-Tanikolide2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Chem. Eur. J 13

      Pages: 5238-5248

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Concise Total Synthesis of (-)-Spongotine A2007

    • Author(s)
      MURAI, Kenichi ; FUJIOKA, Hiromichi
    • Journal Title

      J. Org. Chem. 72

      Pages: 8947-8949

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chiral Auxiliary Multi-Use Methodology : Concise Asymmetric Total Synthesis of (+)-Sch 6423052007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Org. Lett. 9

      Pages: 5605-5608

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective constructions of quaternary carbons and their application to the asymmetric total syntheses of fredericamycin A and discorhabdin A2007

    • Author(s)
      KITA, Yasuyuki ; FUJIOKA, Hiromichi
    • Journal Title

      Pure Appl. Chem. 79

      Pages: 701-713

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-pot synthesis of imidazolines from aldehydes : detailed study about solvent and substrate2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Tetrahedron 63

      Pages: 638-643

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Cerium ammonium nitrate (CAN) for mild and efficient reagent to remove hydroxyethyl unit from 2-hydroxyethyl ether and 2-hydroxyethyl amines2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Tetrahedron 63

      Pages: 625-637

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Reaction of THP-ethers with TESOTf-2,4,6-Collidine Combination : Speculation of the Intermediate, Efficient Deprotection, and Application to Efficient Ring-Closing Metathesis as a Tether2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Adv. Syn. & Cat. (In press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Enantioselective constructions of quaternary carbons and their application to the asymmetric total syntheses of fredericamycin A and discorhabdin A2007

    • Author(s)
      Kita, Yasuyuki, FUJIOKA, Hiromichi et al.
    • Journal Title

      IUPAC, Pure and Applied Chemistry 79(In press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Facile and Efficient Synthesis of Lactols by Domino Reaction of 2,3-Epoxy Alcohols Using Hypervalent Iodine(III) Reagent and Its Application to the Synthesis of Lactones and Asymmetric Synthesis of (+)-Tanikolide2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Chem. Eur. J. 13(In press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Alkyl- and Arylation of Oxacyclic Ethers with Triethylsilyl Trifrate-2,4,6-Collidine-Gilman Reagent Combination : Remarkable Discrimination Of Two Ether Oxygen2007

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Heterocycles 71(In press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Reaction of the Acetals with TESOTf-Base Combination; Speculation of the Intermediates and Efficient Mixed Acetal Formation2006

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 5930-5938

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Lewis Acid Promoted Rearrangement of 2,3-Epoxy Alcohol Derivatives : Stereochemical Control and Selective Formation of Two-types of Chiral Quaternary Carbon Centers from the Single Carbon Skeleton2006

    • Author(s)
      Kita, Yasuyuki, FUJIOKA, Hiromichi et al.
    • Journal Title

      J. Org. Chem. 71

      Pages: 5191-5197

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Highly Chemoselective Alkylation of the Acetals from Aldehydes Using TESOTf-2,4,6-Collidine-Gilman Reagent Combination2006

    • Author(s)
      FUJIOKA, Hiromichi
    • Journal Title

      Synlett 18

      Pages: 3077-3080

    • Related Report
      2006 Annual Research Report
  • [Presentation] 鎖状ジエンケタール類の分子内ハロエーテル化反応の開発2008

    • Author(s)
      藤岡弘道 他 (中原)
    • Organizer
      第128年会 日本薬学会
    • Place of Presentation
      横浜
    • Year and Date
      2008-03-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] 新規ワンポット3成分反応による1,5-ベンゾジアゼピン骨格の構築2008

    • Author(s)
      藤岡弘道 他 (村井)
    • Organizer
      第128年会 日本薬学会
    • Place of Presentation
      横浜
    • Year and Date
      2008-03-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] 超原子価ヨウ素(III)反応剤を用いるβ-アミノアルコール類の酸化的開裂反応の開発とその展開2008

    • Author(s)
      北 泰行 他 (和田)
    • Organizer
      第128年会 日本薬学会
    • Place of Presentation
      横浜
    • Year and Date
      2008-03-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] イミダゾリン新規合成法を利用した海綿由来ビスインドールアルカロイドSpongotine Aの全合成2007

    • Author(s)
      森下、麻衣子
    • Organizer
      大26回メディシナルケミストリーシンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2007-11-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] N-SMase阻害活性を持つスキホスタチンの改良合成法の開発2007

    • Author(s)
      Li, Ruichuan
    • Organizer
      大26回メディシナルケミストリーシンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2007-11-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] NEW THREE-COMPONENT REACTION : FORMATION OF SEVEN-MEMBERED RING BY AN UNEXPECTED REACTION AT THE γ-POTISION OF THE β-KETO ESTERS2007

    • Author(s)
      村井、健一
    • Organizer
      Green Substainable Biological and Chemical Processes
    • Place of Presentation
      大阪
    • Year and Date
      2007-11-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] TOTAL SYNTHESIS OF DISCORHABDIN F, PRIANOSIN B, AND RELATED OXA ANALOGUES BY DEHYDROGENATION AND DETOSYLATION REACTION2007

    • Author(s)
      和田、康史
    • Organizer
      Green Substainable Biological and Chemical Processes
    • Place of Presentation
      大阪
    • Year and Date
      2007-11-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] THPエーテル由来の高次利用を目指した研究2007

    • Author(s)
      久保、大空
    • Organizer
      第27回有機合成若手セミナー
    • Place of Presentation
      京都
    • Year and Date
      2007-11-15
    • Related Report
      2007 Annual Research Report
  • [Presentation] 新規オキソニウムイオン等価体への求核種導入反応2007

    • Author(s)
      沖津、貴志
    • Organizer
      第92回有機合成シンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2007-11-08
    • Related Report
      2007 Annual Research Report
  • [Presentation] 抗腫瘍活性アルカロイドdiscorhabdin類の合成研究2007

    • Author(s)
      和田、康史
    • Organizer
      第33回反応と合成の進歩シンポジウム
    • Place of Presentation
      長崎
    • Year and Date
      2007-11-05
    • Related Report
      2007 Annual Research Report
  • [Presentation] Spongotine Aの全合成研究2007

    • Author(s)
      森下、麻衣子
    • Organizer
      第57回日本薬学会近畿支部大会
    • Place of Presentation
      大阪
    • Year and Date
      2007-10-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] エトキシビニルエステルを介する高効率的ヤクロラクトン化反応の開発2007

    • Author(s)
      高辻、茉由子
    • Organizer
      第57回日本薬学会近畿支部大会
    • Place of Presentation
      大阪
    • Year and Date
      2007-10-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] THPエーテル由来の活性カチオン種を利用する合成法の開発2007

    • Author(s)
      久保、大空
    • Organizer
      第57回日本薬学会近畿支部大会
    • Place of Presentation
      大阪
    • Year and Date
      2007-10-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] アルデヒドからのイミダゾリンの合成法の開発とSpongotine A合成への応用2007

    • Author(s)
      村井、健一
    • Organizer
      第37回複素環化学討論会
    • Place of Presentation
      長野
    • Year and Date
      2007-10-18
    • Related Report
      2007 Annual Research Report
  • [Presentation] New Thee-Component Reaction : Formation of Seven-Membered Ring by an Unexpected Reaction at the γ-Position of the β-Keto Esters2007

    • Author(s)
      村井、健一
    • Organizer
      21^<St> International Congress for Heterocyclic Chemistry
    • Place of Presentation
      シドニー
    • Year and Date
      2007-07-18
    • Related Report
      2007 Annual Research Report
  • [Presentation] Total Synthesis of Discorhabdin F, Prianosin B and Related Oxa Analogues by Dehydraion and Detosylation Reaction2007

    • Author(s)
      和田、康史
    • Organizer
      21^<St> International Congress for Heterocyclic Chemistry
    • Place of Presentation
      シドニー
    • Year and Date
      2007-07-18
    • Related Report
      2007 Annual Research Report
  • [Presentation] 芳香族アルデヒド、エチレンジアミン、β-ケトエステルを用いる新規な3成分反応2007

    • Author(s)
      村井、健一
    • Organizer
      第5回次世代シンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2007-05-25
    • Related Report
      2007 Annual Research Report
  • [Book] Topics in Current Chemistry, "Anthracyclines, Chemistry and Biology"2008

    • Author(s)
      KITA, Yasuyuki ; FUJIOKA, Hiromichi
    • Publisher
      Springer
    • Related Report
      2007 Annual Research Report
  • [Book] 医薬品原薬・中間体製造におけるスケールアップとトラブル対策2008

    • Author(s)
      藤岡,弘道
    • Publisher
      シーエムシー出版
    • Related Report
      2007 Annual Research Report

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Published: 2006-04-01   Modified: 2018-03-28  

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