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

我们为手性中心远离非对映异构衍生官能团的对映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，开发了一种新的手性衍生化试剂(R)和(S)-2A-1P-O-Tf(1)和(R)和(S)-1A-2P-O-Tf(2)，并通过1和2标记获得了2 - 8甲基支链羧酸的手性鉴别。开发了一种新的试剂（R，R）和（S，S）-2A-CH-OH(3)，以改善1和2的缺点，用3进行了2 ~ 24支链的甲基支链脂肪酸的手性鉴别。用该系统测定了样品中神经酰胺、神经节苷和甘油的绝对构型。制备了手性醇（R，R）、（S，S）-2A-CH-COOH(4)和3,4,6- o - ac - 2a -2d-β-Glu-Br(5)的手性衍生化试剂，并建立了用4测定手性醇绝对构型的体系。

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.