| Project/Area Number |
11480159
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Bioorganic chemistry
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| Research Institution | Tohoku University |
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Principal Investigator |
HARADA Nobuyuki Institute of Multidisciplinary Research for Advanced Materials,Tohoku University, Professor, 多元物質科学研究所, 教授 (30006324)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUMOTO Takatoshi Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Research Associate, 多元物質科学研究所, 助手 (50343041)
WATANABE Masataka Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Associate Professor, 多元物質科学研究所, 助教授 (10006330)
門出 健次 東北大学, 多元物質科学研究所, 助手 (40210207)
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| Project Period (FY) |
1999 – 2002
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| Project Status |
Completed (Fiscal Year 2002)
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| Budget Amount *help |
¥14,800,000 (Direct Cost: ¥14,800,000)
Fiscal Year 2002: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2001: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2000: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 1999: ¥5,600,000 (Direct Cost: ¥5,600,000)
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| Keywords | Molecular Chirality / CD Exciton Chirality Method / Absolute Stereochemistry / Chiral Auxiliary / Enantioresolution / X-Ray Crystallography / Chiral Recognition by NMR / %EE Determination by MS / 2-メトキシ-2-(1-ナフチル)プロピオン酸 / 光学純度 / MSスペクトルによる鏡像体過剰決定 / キラルフタル酸法 / HPLC-CD検出計 / CD励起子カイラリティー法 / キラルC60フラーレン / 光学分割の実用化法 / キラルモノアミン / CD補助基 / 分子軌道法計算 / 光学分割能 / 磁気異方性効果 / キラルモノアルコール / 励起子分裂型CD / 分子力場計算 / 分子軌道法 / 配座解析 / 絶対配置 |
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| Research Abstract |
1. We have developed a new strategy for determining the absolute configuration of mono-fucntional compounds by the CD exciton chirality method. This method is powerful for the absolute configurational studies of chiral compounds including natural products.
2. We have recently developed two "powerful chiral acids" for enantioresolution of various alcohols by HPLC on silica gel and also for determination of their absolute configurations by X-ray crystallography and/or by the 1H NMR anisotropy method. The first is the chiral dichlorophthalic acid (-)-1, which was reacted with racemic alcohol to give a diastereomeric mixture of esters. The mixture of esters obtained was separated by HPLC on silica gel, and two separated esters were crystallized respectively to afford single crystals suitable for X-ray analysis. The absolute configuration of the alcohol part was determined by X-ray crystallography of the esters, and enantiopure alcohols were easily recovered by solvolysis with K_2CO_3 in methanol.
3. The second powerful chiral acid is 2-methoxy-2-(1-naphthyl)propionic acid (MαNP acid, (S)-(+)-2 or R-(-)-2) for determining the absolute configuration of chiral alcohols by the 1H NMR anisotropy method.The enantiopure MαNP acid (S)-(+)-2 was allowed to react with racemic alcohols yielding diastereomeric mixtures of esters, which were easily separated by HPLC on silica gel. The NMR signals of diastereomeric esters obtained were fully assigned by the various two-dimensional methods leading to the calculation of Δδ values (Δδ = δ(R,X)-δ(S,X)). By applying the MαNP sector rule, the absolute configuration X was determined. Separated esters were hydrolyzed with KOH/EtOH to recover enantiopure alcohols.
4. Using MαNP acid, (S)-(+)-2 and its deuterium labeled enantiomer R-(-)-2-d_6, we have developed a new diastereomer method for determining enantiomeric excess (% ee) of chiral alcohols by MS spectrometry.
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