Development of highly sensitive system for determination of absolute configuration of natural-products by labelling with chiral fluorescent reagents

开发手性荧光试剂标记测定天然产物绝对构型的高灵敏度系统

• 批准号: 11556019
• 负责人: OHRUI Hiroshi
• 金额: $ 7.1万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11556019/
• 关键词: chiral discrimination; on-line HPLC-exciton CD analysis; determination of absolute configuration; methylation analysis of oligosaccharides; methiy-branched carbosylic acid; methy-branched alcohol; 蛍光性糖骨格誘導化試薬; 遠隔位不斉識別

We have developed a chiral fluorescent labelling reagent, (S)-2-tert-butyl-2-methyl[-], 3-benzodioxole-4-carboxylic acid(1), and determined. the absolute configurations of ciguatoxin and ganbieric acid by the system to use 1 as a labelling reagent. We have also developed a new Chiral analysis method, on-line-HPLC-exciton-CD method using 1 for the determination of absolute configuration of vicinal diols, amino alochols, and diamines. A new highly sensitive methylation analysis system of oligosaccharides that can determine D, L of monosaccharide by labelling with a newly developed (S)-2-methyl-2-β-naphthyl-1, 3-benzodioxole-4-carboxylic acid(2)was developed, and the absolute configuration of a naturalproduct, polycaevenoside A was determined by the system.A new chiral flurorescent labelling reagent, (R, R)-and(S, S)-2-(2, 3-anthrac-enecarboximido)cyclohexanol(3), for the descrimimnation of the chirality at the position remote from the derivatizable carboxyl group was developed. and the absolute configurations of a ceramide and a ganglioside were determined by the system using 3.Further, (R, R)- and(S, S)-2-(2, 3-anthracenedicarboximido)cycloh-exane carboxylic acid(4)and 3, 4, 6-tri-O-acetyl-2-deoxy-2-(2, 3-naphthalenedica-roboximido)-β-D-glucopyranosyl bromide(5)for derivatization of chirai alcohols were developed. A system for the. determination of absolute configuration of chiral alchols with chiral center at the position remote from the hydroxy group was developed.

本文报道了一种手性荧光标记试剂（S）-2-叔丁基-2-甲基[-]，3-苯并间二氧杂环戊烯-4-羧酸（1）的合成及测定。以1为标记试剂的系统测定了雪卡毒素和甘比酸的绝对构型。我们还发展了一种新的手性分析方法-在线-HPLC-exciton-CD法，用于邻位二醇、氨基醇和二胺的绝对构型的测定。本文报道了一种新开发的（S）-2-甲基-2-β-萘基-1，3-苯并间二氧杂环戊烯-4-羧酸（2）标记寡糖的甲基化分析体系，并利用该体系测定了天然产物聚榄香烯苷A的绝对构型。合成了一种新的手性荧光素标记试剂（R，R）-和（S，S）-2-甲基-β-萘基-1，3-苯并间二氧杂环戊烯-4-羧酸（2）。（2，3-蒽甲酰亚胺基）环己醇（3），用于描述远离可衍生羧基位置的手性。用3确定了神经酰胺和神经节苷脂的绝对构型。进一步发展了（R，R）-和（S，S）-2-（2，3-蒽二甲酰亚胺基）环己烷羧酸（4）和3，4，6-三-O-乙酰基-2-脱氧-2-（2，3-萘二甲酰亚胺基）-β-D-吡喃葡萄糖溴（5）用于手性醇的衍生化。一个系统。建立了手性中心位于远离羟基位置的手性醇的绝对构型测定方法。

项目成果

Pu Qian, Hiroshi Nanjo, Toshiro Yokoyama, Toshishige M.Suzuki, Kazuaki Akasaka, and Hiroshi Ohrui: "Chiral molecular patterns of self-assembled ion Pirs composed of(R, S), (S)-16-methyloctadecanoic acid and 4, 4'-bipyridine"Chem.Commun.. 2021-2022 (2000)

Pu Qi、Hiroshi Nanjo、Toshiro Yokoyama、Toshishige M.Suzuki、Kazuaki Akasaka 和 Hiroshi Ohrui：“由(R, S), (S)-16-甲基十八烷酸和 4 组成的自组装离子 Pirs 的手性分子模式，

Kazuaki Akasaka,Seliochlro Imalzuml,and Hiroshi Ohrui: "EnantiomerlcSeparation of Branched Fatty Acids Having Chiral Centers Remote From the Carboxyl Group by labelling with Chiral Fluorescent Derivatization Reagents"Enantiomer. 3. 169-174 (1999)

Kazuaki Akasaka、Seliochlro Imalzuml 和 Hiroshi Ohrui：“通过使用手性荧光衍生试剂标记，分离具有远离羧基的手性中心的支链脂肪酸”对映体。

S.Sato,K.Shimizu,Jeong-Kim,and E.Ami.K.Akasaka,H.Ohrul,and H.Meguro: "Study on the Application of the (S) -2-tert-Buty1-2-methyl-1,3-benzodioxole-4-Carboxylic acid based On-line HPLC-Exciton CD Analysis to Acyclic Vicinal Diols and 1,3-DioIs"Chromatograph

S.Sato,K.Shimizu,Jeong-Kim,E.Ami.K.Akasaka,H.Ohrul,and H.Meguro：“(S)-2-叔丁基1-2-甲基的应用研究

Kazuaki Akasaka and Hiroshi Obrui: "Enantiomeric Separation of Branched Fatty Acids after Conversion withTrans-2-(2,3-Santhra cenedicarbo ximido)cyclohexanol, a Highly Sensitive Chiral Fluorescent Conversion Reagent"Biosci, Biotechnol.Biochem.. 63. 1209-1

Kazuaki Akasaka 和 Hiroshi Obrui：“用高灵敏度手性荧光转化试剂 Trans-2-(2,3-Santhra cenedicarbo ximido)cyclohexanol 转化后支链脂肪酸的对映体分离”Biosci, Biotechnol.Biochem.. 63. 1209-1

K.Akasaka,S.Shitilyukari S.Matsuoka,M.Murata,H.Meguro,and H.Ohrui: "Absolute Configuration of a Ceramidewith a Novel Branched-Chain Fatty Acid Isolated from the Eplphylic Dinoflagellate, Coolja, monotis,"Biosci.Biotechnol.Biochem.,. 64. 1842-1846 (2000)

K.Akasaka、S.Shitilyukari S.Matsuoka、M.Murata、H.Meguro 和 H.Ohrui：“具有从环鞭毛虫、Coolja、monotis 中分离出的新型支链脂肪酸的神经酰胺的绝对构型”Biosci。