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糖錯体およびその類縁体の精密不斉合成への活用

Research Project

Project/Area Number 09874129
Research Category

Grant-in-Aid for Exploratory Research

Allocation TypeSingle-year Grants
Research Field Inorganic chemistry
Research InstitutionTohoku University

Principal Investigator

渡辺 政隆  東北大学, 反応化学研究所, 助手 (10006330)

Co-Investigator(Kenkyū-buntansha) 矢野 重信  奈良女子大学, 理学部, 教授 (60011186)
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1999: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1998: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1997: ¥900,000 (Direct Cost: ¥900,000)
Keywordsグルコース / ラムノース / 配糖錯体 / コバルト / インジウム / 疎水性 / 溶解度 / 有機合成 / 配位錯体 / 親水性 / 不斉合成 / 不斉有機合成 / モノテルペン
Research Abstract

グルコースやラムノースを配位子とするコバルトトリス(2-アミノエチル)錯体は、糖類の酸素を架橋とする複核錯体である。その特異な機能は、これまでの有機合成と大きく異なる反応が期待される。精密有機不斉合成の触媒として活用するには、親水性が強いことが最大の難関である。これらの配糖錯体の機能発現には、糖類の全ての水酸基が必ずしも必要と思われないので、ゴルコースやラムノースの水酸基の幾つかを保護したものを用いて糖錯体の合成を試みたが、それらの精製には至っていない。一方、糖錯体の親水性を弱め疎水性を強めるかわりに、疎水性が弱く、親水性の強い基質を用いればよい。但し、有機合成では生成物の単離・精製をいかに効率良く行うかも大きな課題である。
基質の探索の過程でインジウムを用いて不飽和ケトンを置換基とする高純度のベンゼン誘導体を90%以上の収率で合成することに成功した。これらの不飽和ケトン類を光学分割の素材として活用できた。コバルト錯体の親水性溶媒・疎水性溶媒への溶解度の調整を確立することで、有機合成への利用が期待されることが解明された。

Report

(3 results)
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] 渡辺 政隆: "Enantioresolution and Absolute Stereochemistry of 2-(1-Naphthyl) propane-1,2-diol and Related Compounds"Enantiomer. 4・2. 141-148 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 渡辺 政隆: "Absolute Stereochemistry of 2-Hydroxy-2-(1-naphthyl) propionic Acid as Determined by the ^1H NMR Anisotropy Method"Tetrahedron : Asymmetry. 10・22. 4075-4078 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 渡辺 政隆: "2-Methoxy-2-(1-naphthyl) propionic Acid, a Powerful Chiral Auxiliary for Enantioresolution of their Absolute Configuration by・・・・・"Tehamedron : Asymmetry. (印刷中).

    • Related Report
      1999 Annual Research Report
  • [Publications] 渡辺 政隆: "Enantioresolution by Chiral Phthalic Acid Methode : Absolute Configuration of (2-Methylpheyl) Phenylmethanol and Related Compound"Tetrahedron : Asymmetry. 10・11. 2075-2078 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 渡辺 政隆: "Enantioresolution and Absolute Stereochemistry of o-Substituted Dipheylmethanols"Enantiomer. (印刷中).

    • Related Report
      1999 Annual Research Report
  • [Publications] 渡辺 政隆: "Structural and Chemical Properties of 3,10-Diaza-NN-dimethyl-dispiro [5.0.5.3] penta deca-1.4.8.11-tetraenl"Journal Organic Chemistry. 64・19. 7249-7253 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 渡辺 政隆: "Molecular Chirality by Isotopic Substitution. Syrthesis Absolute Configuration, and CD Spectra of ^<13>C Substituted Chiral Diphenylmethanol"Enantiomer. (印刷中).

    • Related Report
      1999 Annual Research Report
  • [Publications] 渡辺 政隆: "Enantioresolution by Chiral Phthalic Acid Method : Absolute Configurations of Substituted Benzylic Alcohols"Chirality. (印刷中).

    • Related Report
      1999 Annual Research Report
  • [Publications] 渡辺政隆: "Enantioresolution and Absolute Stereochemistry of 2- (1-Naphthyl) propane-1, 2-diol and Related Compounds" Enantiomer. (印刷中). (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 渡辺政隆: "STRUCTURE OF ENDO-2,3-HOMOTROPONEFE (CO) ,AND SYNTHESIS OF OPTICAL ACTIVE ENDO-HOMOHPTAFUL VALENE (CO) ,AND ENDO-HOMOHEPTAFUL VALENEFE (CO) ,DERIVATIVES" Enantiomer. 3・6. 453-461 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 渡辺政隆: "Application of the CD Exiton Chirality Method to Chiral Amines.Use of C_<2y>-Symmetrical 2, -Naphthalenedicarboimide Chromophores" Enantiomer. 2. 197-202 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 渡辺政隆: "A Convenient Synthesis of (1S5S)-4-Alkyl-3-carbomethoxy-6.6-dimethyl-bicyclo[3.1.1]-hept-3-en-2ones with High Optical Purity" Journal Organic Chemistry. 62・9. 2992-2995 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 渡辺政隆: "NMR 13C Satellite signals Useful for the First-Grder Analysis of Conplex Spin Systems" Enautiomer. 2(印刷中). (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 渡辺政隆: "Enanfioresolution and Absolute Stereochemistry of Diarylmethanols" Enentiomer. 2(印刷中). (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 渡辺政隆: "Molecular chirality by I watopic Substitation Synthesis,Absolute configuration and CD spectra of Chiral Diphenylmethanols" Enantiomer. 2(印刷中). (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 渡辺政隆: "Application of th CD Exiton Chiruloty Method Chiral 1,2-Piamines,Use of C_2v-Symmalrical 2,3-Naphtalenedicardoxmido Chranphoc" Enantiomer.

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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