1997 Fiscal Year Annual Research Report

人工受容体を用いた基質分子の絶対配置決定法の開発Mosher法の超分子化

Research Project

Project/Area Number	08874075
Research Institution	Osaka University
Principal Investigator	廣瀬敬治大阪大学, 大学院・基礎工学研究科, 助手 (10252628)
Keywords	光学活性 / クラウンエーテル / アミン / 絶対構造 / 不斉識別 / 温度依存性 / エントロピー / エンタルピー
Research Abstract	人工受容体を用いた基質分子の絶対配置決定法の開発を本研究目的とし、以下の三段階で基質分子の絶対配置決定法の可能性を調べた。その結果、キラルな人工受容体によるキラルなアミンのNon-Enantioselective Complexationという、本研究目的に対する理想的な分子認識系を見いだし、この系を用いてアミンの絶対構造とNMRシフト変化に相関関係のあることを見いだすことが出来た。 (i)基本的分子認識挙動データの集積: 各種人工受容体と不斉アミンの錯形成反応の温度依存性を調べ、熱力学データを集積した。対象とした人工受容体は、光学的に純粋な16種類のキラルクラウンエーテルを用いた。分子認識を伴う錯形成反応をプロトン核磁気共鳴スペクトルを用いた滴定法および紫外可視吸収スペクトルを用いた滴定法、あるいは高速原子衝撃型あるいは電子スプレー型質量分析法によりその挙動を定量的に調べた。見いだされた分子認識挙動を研究成果として研究発表雑誌論文欄記載の文献に発表した。 (ii)人工受容体選定および合成:(i)で用いた16種類の光学活性クラウンエーテルから、エンタルピー・エントロピーの両項がかなり小さくなった人工受容体を特定し、この人工受容体を大量合成した。 (iii)NMR化学シフト変化とアミンの絶対配置との相関関係解明: (ii)で選定し、大量合成した人工受容体を用いて、NMR化学シフト変化とアミンの絶対配置との相関関係を調べ、アミンの絶対配置決定法としての有用性を実証した。

Research Products
(9 results)

All Other

All Publications (9 results)

[Publications] Koichiro Naemura: "Temperature dependence of enantiomer selectivity in the complexations of optically active phenolic crown ethers with chiral amines in solution" Analytical Science. 14. 175-182 (1998)
[Publications] Keiji Hirose: "Temperature dependent inversion of enantiomer selectivity in the complexation of optically active azophenolic crown ethers containing alkyl substituents as chiral barriers with chiral amines" J.Chem.Soc.,Perkin Trans.2. 1649-657 (1997)
[Publications] Kazuko Ogasahara: "Preparation of optically active azophenolic crown ethers containing 1-phenylethane-1,2-diol and 2,4-dimethyl-3-oxapentane-1,5-diol as a chiral subunits : temperature-dependent enantiomer selectivity..." J.Chem.Soc.,Perkin Trans.I. 3227-3236 (1997)
[Publications] Koichiro Naemura: "Preparation of homochiral azophenolic crown ethers containing 1-phenylethane-1,2-diol and 2,4-dimethyl-3-oxapentane-1,5-diol as a chiral subunits : enantiomer recognition behaviour towards chiral 2-aminoethanol" Tetrahedron : Asymmetry. 8. 19-22 (1997)
[Publications] Koichiro Naemura: "Preparation of homochiral phenolic crown ethers having chiral subunits derived from (1R,2S)-cis-1,2,3,4-tetrahydronaphthalene-1,2-diol : temperature^dependent enantiomer selectivity in complexation with neutral" Tetrahedron : Asymmetry. 8. 2585-2595 (1997)
[Publications] Koichiro Naemura: "Preparation of homochiral phenolic crown ethers containing para-substituted phenol moiety and chiral subunits derived from (S)-1-phenylethane-1,2-diol : their chiral recognition behaviour in complexation..." Tetrahedron : Asymmetry. 8. 873-882 (1997)
[Publications] Koichiro Naemura: "Preparation and Enantiomer Recognition Behavior of Azophenolic Crown Ethers containing cis-Cyclohexane-1,2-diol as the Chiral Subunit and 2,4-Dinitrophenylazophenol as the Chromophore" J.Chem.Soc.,Perkin Trans.I. 383-388 (1996)
[Publications] Masami Sawada: "Chiral Molecular Recognition in electrospray ionization Mass Spectrometry" J.Chem.Soc.,Chem.Commun.1735-1736 (1996)
[Publications] Koichiro Naemura: "Temperature dependent reversal of enantiomer selectivity in the complexation of optically active phenolic crown ethers with chiral amines" J.Chem.Soc.,Chem.Commun.2749-2748 (1996)

1997 Fiscal Year Annual Research Report

人工受容体を用いた基質分子の絶対配置決定法の開発Mosher法の超分子化

Principal Investigator

廣瀬 敬治 大阪大学, 大学院・基礎工学研究科, 助手 (10252628)

Research Products

[Publications] Koichiro Naemura: "Temperature dependence of enantiomer selectivity in the complexations of optically active phenolic crown ethers with chiral amines in solution" Analytical Science. 14. 175-182 (1998)

[Publications] Keiji Hirose: "Temperature dependent inversion of enantiomer selectivity in the complexation of optically active azophenolic crown ethers containing alkyl substituents as chiral barriers with chiral amines" J.Chem.Soc.,Perkin Trans.2. 1649-657 (1997)

[Publications] Kazuko Ogasahara: "Preparation of optically active azophenolic crown ethers containing 1-phenylethane-1,2-diol and 2,4-dimethyl-3-oxapentane-1,5-diol as a chiral subunits : temperature-dependent enantiomer selectivity..." J.Chem.Soc.,Perkin Trans.I. 3227-3236 (1997)

[Publications] Koichiro Naemura: "Preparation of homochiral azophenolic crown ethers containing 1-phenylethane-1,2-diol and 2,4-dimethyl-3-oxapentane-1,5-diol as a chiral subunits : enantiomer recognition behaviour towards chiral 2-aminoethanol" Tetrahedron : Asymmetry. 8. 19-22 (1997)

[Publications] Koichiro Naemura: "Preparation of homochiral phenolic crown ethers having chiral subunits derived from (1R,2S)-cis-1,2,3,4-tetrahydronaphthalene-1,2-diol : temperature^dependent enantiomer selectivity in complexation with neutral" Tetrahedron : Asymmetry. 8. 2585-2595 (1997)

[Publications] Koichiro Naemura: "Preparation of homochiral phenolic crown ethers containing para-substituted phenol moiety and chiral subunits derived from (S)-1-phenylethane-1,2-diol : their chiral recognition behaviour in complexation..." Tetrahedron : Asymmetry. 8. 873-882 (1997)

[Publications] Koichiro Naemura: "Preparation and Enantiomer Recognition Behavior of Azophenolic Crown Ethers containing cis-Cyclohexane-1,2-diol as the Chiral Subunit and 2,4-Dinitrophenylazophenol as the Chromophore" J.Chem.Soc.,Perkin Trans.I. 383-388 (1996)

[Publications] Masami Sawada: "Chiral Molecular Recognition in electrospray ionization Mass Spectrometry" J.Chem.Soc.,Chem.Commun.1735-1736 (1996)

[Publications] Koichiro Naemura: "Temperature dependent reversal of enantiomer selectivity in the complexation of optically active phenolic crown ethers with chiral amines" J.Chem.Soc.,Chem.Commun.2749-2748 (1996)

廣瀬敬治大阪大学, 大学院・基礎工学研究科, 助手 (10252628)