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Development of Effective Preparation of Natural α-Tocopherol via Stereoselective Cycloaddition Reaction

Research Project

Project/Area Number 13555252
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Synthetic chemistry
Research InstitutionYOKOHAMA NATIONAL UNIVERSITY

Principal Investigator

INOUE Seiichi  YOKOHAMA NATIONAL UNIVERSITY, FACULTY OF ENVIRONMENT AND INFORMATION SCIENCES, PROFESSOR, 大学院・環境情報研究院, 教授 (90017939)

Co-Investigator(Kenkyū-buntansha) MURAYAMA Toshiyuki  TAKASAGO KOURYOU CO.LTD., CHIEF RESEARCHER, ファイン&アロマケミカル研究所, 主管
HONDA Kiyoshi  YOKOHAMA NATIONAL UNIVERSITY, FACULTY OF ENGINEERING, ASSOCIATE PROFESSOR, 大学院・工学研究院, 助教授 (60231578)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥8,900,000 (Direct Cost: ¥8,900,000)
Fiscal Year 2003: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2002: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2001: ¥5,700,000 (Direct Cost: ¥5,700,000)
KeywordsSALICYLALDEHYDE / VYNYL SULFIDE / 1,4-OXATHIANE / ORTHOQUINONEMETHIDE / FUSED TRICYCLES / FUSED TETRACYCLES / BIOACTIVE CHROMANES / 1, 4-オキサチアン / クロマン
Research Abstract

This Project was undertaken to develop an effective preparation of natural α-tocopherol via stereoselective cycloaddition reaction.
1.As a preliminary examination, synthesis of a primary alcohol containing vinyl sulfide structure was studied and this was successfully obtaind from isobutanal dithioacetal via carbene addition.
2.The reaction of the above mentioned alcohol with salicylaldehyde afforded a new tricyclic 1,4-oxathiane by acid catalyzed cyclization.
3.An sulfide compound for the construction of B/C rings and terpenoid side chain was prepared form phytone via witting reaction and thioacetalization.
4.The cyclization between the terpenoid sulfide and salicylaldehyde afforded a tricyclic compound in a moderate yield. A similar reaction between substituted cyclohexanol instead of acyclic one with salicylaldehyde provided the corresponding tetracyclic compound. The both reactions proceeded with full retention of stereochemistry.
5.Reductive ring opening reaction of the heterocycles thus obtained was successfully achieved by the action of a silyl compound, and bicyclic chromans were obtained in a single step. α-tocol was obtained from the tetracyclic compound containing hydroxyl group at the 2 position of the A ring. The conversion of α-tocol into various tocopherols including α-tocopherol has been known, the above synthesis means a formal total synthesis of tocopherols.

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] S.Inoue, M.Nagao, P.Wang, M.Yamada, K.Honda: "Single-Step Synthesis of Fused Hetero-polycyclic Compounds from Salicylaldehydes and Unsaturated Cyclic Alcohols of Their Sulfur Analogs"Abstracts of 18^<th> International Congress of Heterocyclic Chemistry. 555-555 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Inoue, K.Honda, H.Miyazaki, F.Iwasaki, M.Nagao: "Stereoselective Synthesis of Biologically Active, Fused Oxygen-Heterocycles Based on Pericyclic Reactions"Singapore International Chemical Conference II.Frontiers in Chemical Design and Synthesis. 80-80 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] S.Inoue: "Stereoselective Synthesis of Isoprenoids by Use of Pericyclic Reactions"Abstracts, International Symposium on the Chemistry of Essenntial Oils, Terpenes and Aromatics. 6-9 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 井上 誠一, 本田 清: "多元素縮合多環式化合物の立体選択的合成"化学工業. 55. 212-218 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] INOUE, SEIICHI, et al.: "Single-Step Synthesis of Fused Hetero-polycyclic Compounds from Salicylaldehydes and Unsaturated Cyclic Alcohols and their Sulfur Analogs."Abstracts of 18^<th> International Congress of Heterocyclic Chemistry. 555 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] INOUE, SEIICHI, et al.: "Stereoselective Synthesis of Biologically Active, Fused Oxygen-Heterocycles Based on Pericyclic Reactions."Abstracts of Singapore International Chemical Conference II. 80 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] INOUE, SEIICHI, et al.: "Stereoselective Synthesis of Isoprenoids by Use of Pericyclic Reactions."Abstracts of International Symposium on the Chemistry of Essential Oils, Terpenes and Aromatics. 6-9 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] INOUE, SEIICHI, et al.: "Stereoselective Synthesis of Multi-Element Containing Fused Policyclic Compounds."Chemical Industry. 55. 212-218 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 井上誠一, 土屋文明, 佐藤美智, 王平, 星野雄二郎, 本田 清: "o-キノンメチドの反応性を利用したベンゾピラノオキサチアン及びその類縁体の合成"日本化学会第83春季年会講演予稿集. 1277-1277 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 井上誠一, 土屋文明, 王平, 佐藤美智, 広森修平, 星野雄二郎, 本田清: "o-キノンメチドの反応性を利用した縮合三環式多環式ベンゾピラノオキサチアン及びその誘導体の合成"第46回有機合成化学協会関東支部新潟シンポジウム講演要旨集. 153-154 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 井上誠一, 本田 清: "多元素縮合多環式化合物の立体選択的合成"化学工業. 55・3. 212-218 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] 井上誠一, 土屋文明, 佐藤美智, 王 平, 星野雄二郎, 本田 清: "ο-キノンメチドの反応性を利用したベンゾピラノオキサチアン及びその類縁体の合成"日本化学会大83春季年会講演予稿集. 3H8-3H17 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Inoue: "Stereoselective Synthesis of Isoprenoids by Use of Pericyclic Reactions"Abstracts, International Symposium on the Chemistry of Essential Oils, Terpenes, and Aromatics. S6-S9 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 井上誠一, 土握文明, 王 平, 佐藤美智, 本田 清: "オルトキノンメチド及びそのチオアナログの反応性を利用した硫黄原子を有する縮合多環式化合物の合成"第32回複素環化学討論会講演要旨集. 331-332 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 井上誠一, 土握文明, 王 平, 佐藤美智, 本田 清: "ο-キノンメチドの反応性を利用した縮合三環式ベンゾピラノオキサチアン及びその類縁体の合成"第44回有機合成化学協会関東支部新潟シンポジウム講演要旨集. 121-122 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Inoue, M.Nagao, P.Wang, M.Yamada, K.Honda: "Single-Step Synthesis of Fused Hetero-polycyclic Compounds from Salicylaldehydes and Unsaturated Cyclic Alcohols or Their Sulfur Analogs"Abstracts of 18^<th> International Congress of Heterocyclic Chemistry. 555-555 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 井上誠一: "ペリ環状反応による含酸素複素環化合物の立体選択的合成"日本化学会第80秋季年会講演予稿集. 120-120 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 井上誠一, 王 平, 本田 清: "o-キノンメチドの反応性を利用した単環式化合物から橋頭メチル基を有する含酸素四環式化合物の合成"第42回有機合成化学協会関東支部シンポジウム新潟(長岡)シンポジウム講演要旨集. 117-118 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Inoue, K.Honda, H.Miyazaki, F.Iwasaki, M.Nagao: "Stereoselective Synthesis of Biologically Active, Fused Oxygen-Heterocycles Based on Pericyclic Reactions"Singapore International Chemical Conference II. Frontiers in Chemical Design and Synthesis. 80-80 (2001)

    • Related Report
      2001 Annual Research Report

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

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