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Creation of C2-Symmetric Molecules using An Asymmetric Dihydroxylation and Its Application

Research Project

Project/Area Number 07672260
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionTOYAMA MEDICAL AND PHARMACEUTICAL UNIVERSITY

Principal Investigator

TAKAHATA Hiroki  Faculyof Pharmaceutical Sciences, TOYAMA MEDICAL AND PHARMACEUTICAL UNIVERSITY Associate Professor, 薬学部, 助教授 (00109109)

Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 1996: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1995: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsAsymmetric Dihydroxylation / C_2-Symmetric Molecules / Chiral Auxirality / Enantiomeric Enhancement / Piperidine
Research Abstract

Since chiral C_2-symmetric molecules play an important role in an asymmetric synthesis, much attention has increasingly been focused on their asymmetric synthesis. We describe a promising route to C_2-symmetric tetraols involving the Sharpless asymmetric dihydroxylation (AD) of symmetric terminal dienes and its application to the synthesis of C_2-symmetric chiral amines the representative of chiral auxiliaries of wide use.
The precedent established by the Sharpless group suggested that enantiomeric excess in the case of terminal olefins might be modest (more or less 80% ee). In a symmetrical diene such as the twin olefins conjoined, we anticipate that the stereoselectivity might be improved based on the following consideration : The first AD reaction produces the major and minor enantiomers (diols). Since each enantiomer undergoes the second AD reaction with essentially the same enantiofacial selectivity as in the first AD reaction, three tetraol products result ; a C_2-symmetry compound 1, a meso compound, and ent-1. The overall consequence is that most of the AD reaction resulting from the undesired enantiofacial attack leads to the meso compound. Very little of the mirror image compound ent-1 is formed, and therefore the enantiomeric purity of the major C_2-symmetry product 1 will be high. Based on these consideration, the C_2-symmetric teraols are prepared indeed in high enantiomeric purities from dienes (1,5-hexadiene, 1,6-heptadiene, and ally1 ether). Subsequently, the tetraols are transformed into C_2-symmetric OMICRON-protected alpha, alpha'-bishydroxymethylpyrrolidines, piperidines, and morphorine. Interestingly, we found that medium-pressure chromatography on silica gel of pyrrolidines and piperidines with modest enantioselectivity resulted in efficient enantiomeric fractionation.

Report

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

    (7 results)

All Other

All Publications (7 results)

  • [Publications] Hiroki Takahata Shin-chi Kouno Takefumi Momoke: "New Entry to C_2 Symmetric trans-2.6-Bis (hyhroxymethyl) piperidine Derivatires viathe Sharpless Asymmetric Dihydroxylution" Tefrahedron : Asymmetry. 6.5. 1085-1088 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 高畑廣紀: "非キラルなクロマトグラフィーにおける光学分割現象" 有機合成化学協会誌. 54.8. 708-711 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Hiroki Takahata, Shin-ichi Kouno, and Takefumi Momose: "New Entry to C2 Symmetric trans-2, 6-Bis (hydroxymethyl) piperidine Derivatives via the Sharpless Asymmetric Dihydroxylation" Tetrahedron : Asymmetry. 6-5. 1085-1088 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Hiroki Takahata: "Resolution of Excess Enantiomers with Achiral Phase Chromatography" Organic Synthetic Chemistry, JPN. 54-8. 708-711 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] HIROKI TAKAHATA,Shin-ichi Konno,Takefnmi Momose: "New Entry to C_2 Symmetric trans-2,6-Bis (hydroxymethyl) piperidine Derivatires via the Sharpless Asymmetric Dihydroxyeation" Tetrahedron : Asymmetry. 6・5. 1085-1088 (1995)

    • Related Report
      1996 Annual Research Report
  • [Publications] 高畑廣紀: "非キラルなクロマトグラフィーにおける光学分割現象" 有機合成化学協会誌. 54・8. 708-711 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.TAKAHATA: "New Entry to C_2 Symmetric trans-2,6-Bis(hydroxy methyl)-piperidine Derivatives via the Sharpless Asymmetric Dinydroxylation" Tetrahedron: Asymmetry. 6. 1085-1088 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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