手性试剂TMPEA用于手性酮对映体纯度测定的研究

β-三氟甲基-β甲氧基β-苯基乙胺（TMPEA）是含氨基功能团的手性试剂[1]．由于胺可将按酸转变成酸胺，该试剂已成功地用于手性有机酸对映体的纯度测定[2]．考虑到胺同样可将醛酮转变成亚胺，本文进一步探讨了TMPEA用于手性醒酮对映体纯度测定的可行性．用R－（－）－TMPEA及dl－TMPAE分别与下列4种手性酮反应，制备相应的非对映异构亚胶：比较光活亚胺及相应的非对映异构体混合物亚腔的NMR谱，可确定各组非对映异构亚胺‘HNMR位移差（以OCH为探针基团）和’‘FNMR的位移差（以CF为探针基团）（表1）．TablelCheffiicalshif…     

Enantioseparation in capillary electrophoresis using 2-O-(2-hydroxybutyl)-beta-CD as a chiral selector

The resolving ability of 2-O-(2-hydroxybutyl)-beta-CD (HB-beta-CD) with different degrees of substitution (DS = 2.9 and 4.0) as a chiral selector in CZE is reported in this work. Fourteen chiral drugs belonging to different classes of compounds of pharmaceutical interest such as beta-agonists, antifungal agents, ageneric agents, etc., were resolved. The effects of the DS of HB-beta-CD on separations were also investigated. The chiral resolution (R(s)) was strongly influenced by the concentrations of the CD derivative, the BGE, and the pH of the BGE. Under the conditions of 50 mmol/L Tris-phosphate buffer at pH 2.5 containing 5 mmol/L HB-beta-CD, all 14 analytes were separated. The very low concentration necessary to obtain separation was particularly impressive. The DS had a significant effect on the resolution of the chiral drugs and the ionic strength of the separation media; hence, the use of a well-characterized CD derivative is crucial.     

Direct determination of the enantiomeric purity of oxyphenonium using chiral HPLC with post-column extraction detection

Summary A method is described for the determination of the enantiomeric purity (enantiomeric excess) of the anticholinergic drug oxyphenonium. The method for this quaternary ammonium compound is based on the direct HPLC analysis with a chiral stationary phase. Two kinds of 1-acid glycoprotein-bonded phases were used.For the detection a post-column extraction with fluorescence detection of the ion-pair counter ion dimethoxyantracene sulphonate was used.     

符合经典构效关系的抗肿瘤铂类药物

综述了自顺铂、卡铂后符合经典构效关系的铂类抗肿瘤药物的发展概况，按载体配基和离去基团的结构特征进行了分类，总结了各类配合物的构效关系和临床进展，其中重点对手性二胺配体的铂(Ⅱ)配合物进行了介绍。并讨论了顺铂、卡铂、奥沙利铂的作用机理。     

Chiral separation of β-amino alcohols by capillary electrophoresis using cyclodextrins as buffer additives. I. Effect of varying operating parameters

Summary Capillary electrophoresis has been used for the chiral analysis of two -amino alcohol pharmaceutical compounds. Capillary zone electrophoresis conditions were used with -cyclodextrin as a chiral mobile phase additive. The effects of variation of -cyclodextrin concentration, temperature, pH, background electrolyte composition and concentration have been investigated. Optimum separations were achieved for clenbuterol using -cyclodextrin at its solubility limit (16mM), the lowest practicable temperature (19°C), pH 4.0 and an electrolyte solution with a high ionic strength prepared from 0.1 M citric acid and 0.3 M Na₂HPO₄. For the development compound picumeterol and its (S)-enationmer, the optimum pH 4.0 buffer was prepared from 0.1 M citric acid and 0.2 M sodium acetate. Baseline separation with resolution greater than 2 was achieved for both compounds.This work was presented in part at the 2nd International Symposium on Chiral Discrimination, Rome, May 27–31, 1991.     

(1R,2S)或(1S,2R)-1,2-二苯基-2-氨基乙醇衍生物手性配体的合成及其用于不对称催化反应

重点报道了以（１Ｒ，２Ｓ）或（１Ｓ，２Ｒ）－１，２－二苯基－２－氨基乙醇衍生物手性配体的合成及其用于不对称催化反应的研究，如去氢氨基酸的氢化、醛的乙基锌加成、酮的还原、活泼亚甲基化合物的烷基化、醛的硅腈化和瑞福马斯基反应等．研究了手性配体的结构、底物和反应条件等对上述反应的对映选择性和催化活性的影响．     

Arylcarbamoylated allylcarbamido-β-cyclodextrin: synthesis and immobilization on nonfunctionalized silica gel as a chiral stationary phase

Four new chiral stationary phases based on mono-(6^A-allylcarbamido-6^A-deoxy)-arylcarbamoylated β-cyclodextrin were synthesized. The chiral stationary phase of phenylcarbamoylated β-cyclodextrin exhibited excellent separation capability for a variety of chiral compounds. Compared with the previous work, it was found that the spacer remained on the surface of the silica gel and decreased the enantioseparation capability.     

Helical structures architecture of l-{2-(4-hydroxy-phenyl)-1-[(pyren-1-ylmethyl)-carbamoxyl]-ethyl}-carbamic acid tert-butyl ester

A new pyrenemethylamine substituted l-Boc-tyrosine derivative was synthesized and characterized. UV-vis, FL, CD, and light scattering experiments proved that the chiral molecules were able to self-assemble for formation of new aggregate structure. The SEM and AFM images indicated that the helical wires could be fabricated by π-π stacking interaction between adjacent pyrene molecules.     

An efficient and stereodivergent synthesis of threo- and erythro-β-methylphenylalanine. Resolution of each racemic pair by semipreparative HPLC

threo and erythro diastereoisomers of the constrained amino acid (βMe)Phe can be obtained separately on a multigram scale through a three-step synthesis from the corresponding Z and E isomers of 2-phenyl-4(α-phenylethylidene)-5(4H)-oxazolone. The 5(4H)-oxazolones are readily available from acetophenone and hippuric acid. The four enantiomerically pure isomers of β-methylphenylalanine, (2R,3R)-(βMe)Phe, (2S,3S)-(βMe)Phe, (2R,3S)-(βMe)Phe and (2S,3R)-(βMe)Phe, have been prepared by HPLC resolution of the racemic precursors methyl threo (or erythro)-2-benzamide-3-phenylbutanoates.     

Convenient synthesis of mono(6-N-allylamino-6-deoxy)permethylated β-cyclodextrin: a promising chiral selector for an HPLC chiral stationary phase

Mono(6-(p-toluenesulfonyl))permethylated β-cyclodextrin, a versatile precursor for a wide variety of mono-functionalized permethyl β-cyclodextrins, has been generated successfully by the direct methylation of monotosylated cyclodextrin. This afforded a convenient synthesis of mono(6^A-N-allylamino-6^A-deoxy)permethylated β-cyclodextrin. Hydrosilylation of the chiral selector with (EtO)₃SiH and reaction of the resultant reactive siloxane with pristine silica gel afforded a facile entry into a structurally well-defined chiral HPLC stationary phase.