Development of chiral fluorescent derivatization reagents for discrimination of enantiomers having chiral centers far remote from the derizatizable functional groups and their application to determination of absolute configuration of natural products

手性荧光衍生试剂的开发，用于区分手性中心远离可衍生官能团的对映体，及其在天然产物绝对构型测定中的应用

• 批准号: 10460046
• 负责人: OHRUI Hiroshi
• 金额: $ 6.34万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10460046/
• 关键词: discrimination of remote chirality; branched fatty acid; branched alcohol; chiral discrimination; fluorescent chiral derivatization reagent; ^1H-NMR; HPLC; 蛍光性不斉誘導化試薬; 高感度蛍光検出; (S)-2AP-OTf; (S)-1A2P-OTf; CH-π相互作用; ゴーシュ効果

We have open a way to the chiral discrimination of enantiomers having chiral center far remote from the diastereomeric-derivatizable functional groups that has been thought impossible for long time. Thus, a new chiral derivatization reagents, (R)-and (S)-2A-1P-O-Tf (1) and (R)-and (S)-1A-2P-O-Tf (2) are developed and the chiral discriminations of the carboxylic acids with methyl branching at from 2 to 11 by ^1H-NMR and those from 2 to 8 by HPLC were attainedby labelling with 1 and 2. A new reagent to improve the shortcomings of 1 and 2, (R,R)-and (S,S)-2A-CH-OH (3), was developed and the chiral discrimination of methyl branched fatty acids with branching from 2 to 24 was attained with 3. By these system, the absolute configuration of ceramides, gangliosides, and glycerol were determined using μ〜ng of samples.Chiral derivatization reagents for chiral alcohols (R,R)-and (S,S)-2A-CH-COOH (4) and 3,4,6-O-Ac-2A-2d-β-Glu-Br (5) were prepared, and a system for the determination of absolute configuration of chiral alcohols by use of 4 was developed.

我们为手性中心远离非对映异构体衍生化官能团的对映异构体的手性鉴别开辟了一条长期以来被认为是不可能的途径。因此，我们研制了一种新的手性衍生试剂，（R）-和（S）-2A-1 P-O-Tf（1）和（R）-和（S）-1A-2 P-O-Tf（2），并通过标记1和2，获得了2 - 11位甲基支化羧酸和2 - 8位甲基支化羧酸的1H-NMR手性鉴别和HPLC手性鉴别。改进了1和2的缺点，研制了一种新试剂（R，R）-和（S，S）-2A-CH-OH（3），并用3实现了对2 - 24个支链的甲基支链脂肪酸的手性鉴别。制备了手性醇（R，R）-和（S，S）-2A-CH-COOH（4）和3，4，6-O-Ac-2A-2d-β-Glu-Br（5）的衍生试剂，并建立了用4测定手性醇绝对构型的体系。

项目成果

Kazuaki Akasa,Hiroshi Meguro,and Hiroshi Ohrui: "Enantiomeric Separation of Carboxylic Acids Having Chiral Centers Remote from the Carboxyl Group by Labelling with a Chiral Fluorescent Derivatization Reagent"Tetrahedron Letters. 38. 6853-6856 (1997)

Kazuaki Akasa、Hiroshi Meguro 和 Hiroshi Ohrui：“通过手性荧光衍生试剂标记具有远离羧基的手性中心的羧酸的对映体分离”四面体字母。

Kazuaki Akasaka, Keiichiro Imaizumi, and Hiroshi Ohrui: "Enantiomeric Separation of Branched Fatty Acids having chiral centers remote from the carboxyl group by derivatization with chiral fluorescent-labellig reagents"BUNSEKI KAGAKU. 48. 1085-1094 (1999)

Kazuaki Akasaka、Keiichiro Imaizumi 和 Hiroshi Ohrui：“通过使用手性荧光标记试剂进行衍生化，对具有远离羧基的手性中心的支链脂肪酸进行对映体分离”BUNSEKI KAGAKU。

Kazuaki Akasa, Hiroshi Ohrui: BUNSEKI. 11. 678-683 (2000)

赤狭和明、大流井宏：文色。

大類洋: "蛍光分析試薬の開発とその応用-油化学研究を中心として-"油化学. 44. 949-959 (1995)

大井浩：“荧光分析试剂的开发及其应用——以石油化学研究为主”《石油化学》44。949-959（1995）。

Hiroshi Meguro and Hiroshi Ohrui: "Strategy and Design of Novel Reagents for the Fluorometric Analysis of Biomelecule"Biosci,Biotechnol. Biochem... 60. 1919-1924 (1995)

Hiroshi Meguro 和 Hiroshi Ohrui：“生物分子荧光分析新型试剂的策略和设计”Biosci，Biotechnol。