Chiral soluble polymers and microspheres for enantioselective crystallization

A series of chiral polymers based on poly(N‐acryl) amino acids was synthesized using a convergent synthetic approach. These chiral polymers have been used as chiral additives to induce enantioselective crystallization of racemic or conglomerate amino acids in solutions. These polymeric additives showed strong capabilities to enhance highly enantioselective resolution during the crystallization of amino acids. In addition, these polymers caused unusual modifications of amino acid crystal morphologies. Furthermore, spherical microparticles of those same chiral polymers were also shown active in similar chiral discriminations during amino acid crystallizations occurring on microparticle surfaces. Our study demonstrates the high potential of chiral polymers and microparticles to resolve amino acids throughout crystallization processes. High enantiomeric excesses in one targeted enantiomer of amino acids can also be maximized via time‐dependent kinetic control of crystallizations. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3009–3017, 2006     

使用手性相转移催化剂合成D-苯丙氨酸

目前,氨基酸不对称合成方法甚多,但是使用手性相转移催化剂未见有报道。本文报道在同位素标记氨基酸不对称合成研究中,用非标记甘氨酸进行模型试验的初步结果:使用(-)-氯化-N-苄基辛可尼丁鎓作催化剂,可获得近90%光学纯度的 D-苯丙氨酸,化学产率61.6%。     

New Chiral Kemp's Acid Diamides for Chiral Amine Recognition by 1 H NMR

Two Kemp's acid diamides were synthesized and applied to chiral amine recognition using ¹H NMR analysis. One derivative based on 1-(1-naphthyl)ethylamine had good chiral recognition of six amines and was useful to determine the optical purity for three amines, i.e., methylbenzylamine, 1-(1-naphthyl)ethylamine and 1- henylpropylamine,however, the cyclohexylethylamine derivative showed little discrimination for the amines studied. Together with the results for alkylamines, it was shown that aromatic structure was important for aromatic shielding anisotropy and –– interactions between host and guest. The structure of the 1-(1-naphthyl)ethylamine derivative in solution was also considered based on ¹H NMR data and computer simulation.     

手性配体立体选择性萃取分离扁桃酸对映体

Based on chiral ligand exchange, the distribution behavior of mandelic acid enantiomers in the two-phase system containing copper ion(Ⅱ)(Cu²⁺) and N-n-dedecane-L-hydroxyproline (L), was studied. At different pH, the partition of Cu²⁺ in the two-phase system containing N-n-dedecane-L-hydroxyproline, was investigated. The formation constant of binary cpmplex(Li₂Cu) was obtained by regression. The influence of pH, concentrations of Cu²⁺ and chiral ligand, and solvents on partition coefficients(K) and separation factor(α), was discussed. The experimental results show that Li forms more stable ternary complex with D-mandelic acid than with L- mandelic acid. There is a large influence of pH on K and α. At low pH values (<3.5), formation of binary complexes is thermodynamically unfavourable. K and α are best when pH values are above 3.5 and the molar ratio of chiral ligand to Cu²⁺ is 2∶1. At the same time, solvents influence K and α very much.     

N-烷基化手性氨基醇配体的合成

本实验制备了不同构型的两种N-单烷基和N-双烷基的新的手性氨醇配体。     

Synthesis and Characterization of Chiral Binuclear Organolanthanide and Yttrium Alkoxides Containing Cyclopentadienyl Ligand

Recently,variousdimericlanthanidealkoxidesofthetype[(Ln(p-oR)(Cp)2}2]havebeenpreparedbytreatmentofthechlorocomplexeswithsodiumalkoxideslorprotonationofLn(Cp)3withstoichiometricamountsofalcohols2.Butthechiralorganolanthanidepolymericalkoxidescontainingcyclopentadienylgroupsandopticallypurediolligandshavenotbeenreporteduptonow3.Furthermore,themethodofprotonationisusuallyappliedinnon-coordinatingsolventssuchasheptane,hexane,benzeneandtoluene.Inthispaper,wewishtoreportthefirstsynthesisofchiralcy…     

Chiralcel OD-RH手性柱拆分卡维地洛对映体

采用Ch iralcelOD-RH(纤维素3,5-二甲基苯基氨基甲酸酯)手性固定相高效液相色谱法研究了乙腈-高氯酸钠缓冲盐体系对卡维地洛的手性拆分情况,讨论了流动相的各个因素(有机相的种类和比例、缓冲盐浓度、酸度等)对手性拆分的影响。在乙腈-高氯酸钠缓冲盐(pH 5.5,50 mmol/L)的体积比为35∶65的色谱条件下,卡维地洛对映体获得了基线分离。     

Enantioseparation of Novel Chiral Tetrahedral Clusters on a Chiral Stationary Phase (CSP) by High Performance Liquid Chromatography

In recent years, the synthesis of chiral tetrahedral clusters has been studied extensively and various types are accessible , which are a kind of organometallic compounds with greatly growing interest due to their potential application to asymmetric reaction catalysts. As an efficient     

LC Packing Materials for Pharmaceutical and Biomedical Analysis

 The author has prepared novel liquid chromatography (LC) packing materials for pharmaceutical and biomedical analysis. Those include LC packing materials for direct serum injection assays of drugs and their metabolites, LC packing materials for resolution of enantiomeric drugs, and uniformly sized molecularly imprinted polymers for drugs and their metabolites.