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.

我们已经开发了一种手性荧光，（S）-2-tert-butyl-2-甲基[ - ]由雪茄毒素和ganbieric酸的绝对构型，也开发了一种新的手性分析方法，即对VICINAL DIOL的绝对构型，氨基二醇，氨基Alochols和Diamines。 A由系统确定。一种新的手性r） - 和（s，s）-2-（2，2，2，3-anththrac-enecarboximido）环己醇（3），以描述远离可衍生的羧基的位置的描述使用3.further，（R，R）和（S，S）-2-（2，2，3-含次持平的辅助辅助因子），由系统确定了神经酰胺和神经节的开发。和3、4、6-三 - 乙酰基-2-（2、3-萘二烯丙基 - 耐氧氧化物O） - β-D-葡萄糖基溴化溴（5）用于衍生化的Chirai醇。开发了远离羟基的位置。

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

Kumi Shimizu, Jeoong-Hwan Kim, Kazuaki Akasaka and Hiroshi Ourui: "Application of(S)-TBMB Carboxylic Acid-Based On-lineHPLC-Exciton-CD Analysis to Acyclic Vicinal Aicohols and Amino Alcohols"Chirality. 11. 149-159 (1999)

Kumi Shimizu、Jeoong-Hwan Kim、Kazuaki Akasaka 和 Hiroshi Ourui：“基于(S)-TBMB 羧酸的在线 HPLC-激子-CD 分析无环邻位醇和氨基醇的应用”手性。

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