2006 Fiscal Year Final Research Report Summary
Highly sensitive enantiomeric discrimination of chiral branched alkyl chains of fatty alcohols and amines, and the application to determine absolute stereochemistry of natural occurring products
| Project/Area Number |
16380076
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Bioproduction chemistry/Bioorganic chemistry
|
|---|
| Research Institution | Tohoku University |
|---|
Principal Investigator |
AKASAKA Kazuaki Tohoku University, Graduate School of Life Sciences, Associate Professor, 大学院生命科学研究科, 助教授 (10201881)
|
|---|
| Project Period (FY) |
2004 – 2006
|
| Keywords | Chiral alcohols / Chiral amines / Enantiomeric discrimination / High performance liquid chromatography / Fluorescence derivatization / Insect pheromones / Nuclear magnetic resonance / Stereochemistry |
|---|
| 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.
… More
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
|
Research Products
(16 results)
-
-
-
-
-
-
-
-
[Journal Article] Absolute Stereochemistry of Fungal Beauveriolide III and ACAT Inhibitory Activity of Four Stereoisomers2006
Author(s)
Ohshiro, T., Namatame, I., Nagai, K., Sekiguchi, T., Doi, T., Takahashi, T., Akasaka, K., Rudel, L.L., Tomoda, H., Omura, S.
-
Journal Title
Journal of Organic Chemistry 71
Pages: 7643-7649
Description
「研究成果報告書概要(欧文)」より
-
-
-
-
-
-
-
-
[Journal Article] Synthesis of four stereoisomers of 2,6-dimethyloctane-1,8-dioic acid, a component of the copulation release pheromone of the cowpea weevil, Callosobruchus maculates2005
Author(s)
Tomonori Nakai, Arata Yajima, Kazuaki Akasaka, Takayuki Kaihoku, Miki Ohtaki, Tomoo Nukada, Hiroshi Ohrui, Goro Yabuta
-
Journal Title
Bioscience, Biotechnology and Boichemistry 69(12)
Pages: 2401-2408
Description
「研究成果報告書概要(欧文)」より
