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Development and Application of <C_2> -Symmetrically Substituted Pyrrolidine Chiral Auxiliaries

Research Project

Project/Area Number 59470020
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 天然物有機化学
Research InstitutionKyushu University

Principal Investigator

YAMAGUCHI Masaru  Professor, Faculty of Science, Kyushu University, 理学部, 教授 (60037140)

Co-Investigator(Kenkyū-buntansha) INANAGA Junji  Assistant, Faculty of Science, Kyushu University, 理学部, 助手 (50091244)
KATSUKI Tsutomu  Assistant, Faculty of Science, Kyushu University, 理学部, 助手 (40037271)
OKUKADO Nobuhisa  Assistant Professor, Faculty of Science, Kyushu University, 理学部, 助教授 (40037213)
Project Period (FY) 1984 – 1986
Project Status Completed (Fiscal Year 1986)
Budget Amount *help
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1986: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1985: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1984: ¥5,200,000 (Direct Cost: ¥5,200,000)
Keywords2,5-Disubstituted Pyrrolidines / <C_2> -Symmetry / Asymmetric Reaction / [2,3]Wittig Rearrangement / 立体選択的反応 / 〔2,3〕Wittig転位
Research Abstract

Effective asymmetric reactions with 2,5-disubstituted pyrrolidines as chiral auxiliaries and related stereoselective reactions were developed.
The aldol condensation of the amide enolates derived from these amides, with aldehydes proceeded with high diastereo (>60:1) and diastereoface (>95% de) selectivities, when the corresponding zirconium enolates were used. Zirconium enolates derived from (E)-alkenyloxyacetyl amides, exhibited high level of syn-diastereo (>28:1) and diastereoface (>95% de) selectivities in their [2,3]Wittig rearrangement reaction. Zirconium mediated [2,3]Wittig rearrangement of (E)- <alpha> -alkenyloxyacetic acid esters was also performed with syn-diastereoselectivity (>50:1), high level of chirality transfer (-100%), and exclusive formation of (Z)-double bond. A combination of this [2,3]Wittig rearrangement reaction and Peterson reaction provided a highly stereoselective approach to (E,Z)- and (Z,Z)-dienes. Further, zirconium mediated enolate Claisen rearrangement was found to proceed through a boat-like transition state, differing from the usual [3,3]sigmatropic rearrangements which proceed through a chair-like transition state.
Some of these reactions were applied to the synthesis of natural products. Informations obtained through these studies are considered to contribute to the development of acyclic stereocontrol.

Report

(1 results)
  • 1986 Final Research Report Summary
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] 香月勗: Tetrahedron Letters. 26. 5807-5810 (1985)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 池上悟: Tetrahedron Letters. 27. 3403-3406 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 内川昌子: Tetrahedron Letters. 27. 4577-4580 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 内川昌子: Tetrahedron Letters. 27. 4581-4582 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 内山春美: Chemistry Letters. 351-354 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 黒田聡: Tetrahedron Letters. 28. (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 香月勗: Chemistry Letters.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] 香月勗: 有機合成化学協会誌. 44. 532-544 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Tsutomu Katsuki: "Asymmetric Aldol Reaction of Amide Enolates Bearing trans-2,5-Disubstituted Pyrrolidines as Chiral Auxiliaries" Tetrahedron Letters. 26. 5807-5810 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Satoru Ikegami: "Asymmetric Synthesis of <alpha> -Amino Acids by Alkylation of a Glycine Amide Derivative Bearing Chiral 2,5-Disubstituted Pyrrolidine as an Amine Component" Tetrahedron Letters. 27. 3403-3406 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Masako Uchikawa: "Asymmetric [2,3]Wittig Rearrangement of 2'-Alkenyloxyacetamide Bearing trans-2,5-Bis(methoxymethoxymethyl)pyrrolidine Moiety as a Chiral Auxiliary" Tetrahedron Letters. 27. 4577-4580 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Masako Uchikawa: "[2,3]Wittig Rearrangement of 2'-Alkenyloxyacetic Acid Esters" Tetrahedron Letters. 27. 4581-4582 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Harumi Uchiyama: "Ester Enolate Claisen Rearrangement via Boat-Like Transition State" Chemistry Letters. 351-354 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Satoru Kuroda: "Stereoselective Synthesis of (2E,4Z)-Dien-1-ols; Key Intermediates for Synthesis of Sex Pheromones of Silk Worm and Grape Vine Moth" Tetrahedron Letters. 28. (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Tsutomu Katsuki: "Synthesis of Enantiomerically Pure Tedanolide Side Chain" Chemistry Letters.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Tsutomu Katsuki: "Asymmetric Reactions Using <C_2> -Symmetrically 2,5-Disubstituted Pyrrolidines as Chiral Auxiliaries" Journal of Synthetic Organic Chemistry Japan. 44. 532-544 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary

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Published: 1987-03-31   Modified: 2016-04-21  

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