| Budget Amount *help |
¥9,900,000 (Direct Cost: ¥9,900,000)
Fiscal Year 2006: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2005: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2004: ¥6,400,000 (Direct Cost: ¥6,400,000)
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| Research Abstract |
(1R,2R)-and (1S,2S)-2-(2,3-Anthracenedicarboximide)cyclohexane carboxylic acids were developed as chiral fluorescent derivatization reagents. The reagents made it possible to discriminate the chirality of branched alkyl chain of primary and secondary alcohols having a chiral methyl branch remote from the hydroxyl group with at least 8 methylene spacers. Especially the HPLC method made it possible to discriminate their chirality with 10^<-15> mole levels by fluorometric detection. The reagents also made it possible to discriminate chirality of secondary alcohols by both the ^1H-NMR and the reversed-phase HPLC. Since chiral secondary alcohols having a methyl branched alkyl chain were separated into more than 3 peaks by the reversed-phase HPLC, it was possible to discriminate the chirality of the hydroxyl group and the alkyl branch simultaneously. Similarly, it was possible to discriminate chirality of amines having a chiral branched alkyl chain by using the acid chloride of the reagents.
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The combination of derivatization method using these reagents and 2D-HPLC were successfully applied to determine the absolute configurations and stereoisomers constitution of insect pheromones of the screw warm fly, Cochliomyia hominivorax, and the cowpea weevil, Callosobruchus maculate, respectively. Moreover, doubly checking method by using both enantiomers of the reagents was very useful to confirm the results.
We also synthesized new chiral fluorescence labeling reagents having a 2,3-anthracenedicarboximide group from D-glucosamine, and it was possible to introduce target alcohols at the anomeric positions of the reagents with β-selectivity by glycosidations. Especially, it was possible to use methyl glycoside reagent as a glycosyl donor with a Lewis acid and microwave irradiation, and it gave selectively β-glycoside while the reaction without microwave irradiation gave α-and β-mixed glycosides. Those reagents showed very high chiral discrimination ability, and they made it possible to separate the eight stereoisomers of 4,8,12,16-tetramethylheptadecanol and a-tocopherol by HPLC after derivatizations. Less
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