手性噁唑啉的合成及其在不对称还原反应中的应用

由多元羧酸和手性2-氨基-1-丁醇经由相应的多元酰胺醇缩合制备了6个新型手性多噁唑啉,其结构经1H NMR谱、IR谱、MS谱和元素分析确证;并应用这些手性多噁唑啉配体,初步探讨了苯乙酮在KBH4或NaBH4作用下的不对称还原反应.     

潜手性Schiff碱不对称催化还原反应研究进展

对近年来潜手性Schiff碱的不对称催化氢化的发展状况按照均相、非均相及氢转移催化氢化三种类型进行了较为详尽的综述.     

手性钯络合物催化下2-硝基环酮的不对称烯丙基化反应

在用氮杂冠醚改良的手性二茂铁膦与钯的络合物催化下, 2-硝基环酮可进行不对称烯丙基化反应. 讨论了配位基的形状, 反应物的构造, 碱的类型以及反应时间对反应速率和立体选择性的影响. 通过增加反应的空间位阻改进了反应的立体选择性 .     

中性配合物Cr(acac)_3、mer-和fac-[Cr(bza)_3]的光学拆分

本文用新方法合成了Cr(bza)_3,改进了其mer-、fac-异构体的分离方法;增大了Cr(acac)_3的化学拆分量(1.5g)。试制了DBT(二苯甲酰-d-酒石酸)吸附型手性固定相(CSP),并成功地用于色谱拆分标题配合物的对映体,mer-[Cr(bza)_3]的部分拆分是首次发现的,其他配合物的拆分结果均优于文献方法。根据mer-[Cr(bza)_3)拆分流出液前、后组分的CD光谱,指定了其对映体绝对构型。还讨论了DBT吸附型CSP的拆分效能和色谱特性。     

Chiral recognition in aqueous solutions. Preferential configurations of α-aminoacids bearing substituted alkyl chains at 25°C

Calorimetric measurements were carried out at 25°C on binary and ternary aqueous solutions containing L and D forms fo the following -aminoacids: tryptophan, cysteine, methionine, phenylalanine, histidine, threonine, and citrulline, which contain both hydrophilic and hydrophobic domains. Differences were found between the values of the homochiral and heterochiral pairwise enthalpic interaction coefficients for tryptophan, cysteine, and methionine. To the contrary, chiral recognition was not detected for phenylalanine, histidine, citrulline, and threonine. The data were interpreted in terms of a preferential configuration model. Chiral recognition is detected only when the interactions of the side chains in the homo- and heterochiral configurations are different. Chiral recognition disappears when a competition exists between zwitterion-zwitterion interactions and side chain-side chain interactions. In some cases, such as for citrulline, compensation effects can occur due to thermal contributions from different domains which mask chiral recognition.     

氧氟沙星片剂和滴眼液中氧氟沙星对映体的毛细管电泳拆分及定量分析

采用环糊精及其衍生物为手性选择剂在CE上对氧氟沙星对映体进行了分离，研究了环糊精种类、浓度、分离电压、温度对分离的影响．重点考察了氧氟沙星的定量线性范围、检测限和重现性，在20-200mg／L浓度范围内，迁移时间重现性的相对标准偏差(RSD)控制在1．13％以内，峰面积重现性的RSD控制在4．3％以内，检测限为1mg／L．结果表明用20mmo1／L二甲基-β-环糊精(DM-β-CD)为手性选择剂，背景电解质为50mmo1／L Na2HPO4，pH＝3．0，不加有机添加剂情况下可得到较好的分离效果．同时，对氧氟沙星药品实样进行了分析，建主了一种市售氧氟沙星片剂和滴眼液中氧氟沙星对映体简单、快速的毛细管电泳分离、定量分析方法．     

相变温度低且宽的含有胆甾烯基和反式-4-烷基环己基苯氧基的二介晶化合物

Unsymmetrical dimesogenic compounds with cholesteryl and 4-（trans-4-n-alkylcyclohexyl）phenoxy parts were synthesized by condensation of cholester-3-yl 6-bromohexanoate with appropriate 4-（trans-4-n-alkylcyclohexyl）- phenols. Structures and thermal phase behaviour of these dimesogenic compounds have been confirmed by IR, IH NMR, elemental analysis, DSC, polarity microscopy and XRD measurements. Their thermal phase behaviour was significantly different with that of other cholesterol-based dimesogens while they exhibited low and wide phase transition temperature.     

双冠醚研究(Ⅳ)——Schiff碱型和仲胺型双-(苯并15冠-5)对碱金属苦味酸盐的萃取行为

仲胺型双冠醚与四苯硼酸碱金属盐在丙酮溶液中。25℃下的电导说明它们与Na~+可能形成1∶1络合物(冠醚单元∶金属离子),而与K~+、Rb~+、Cs~+离子则形成2∶1络合物。用Schlff碱型和仲胺型双-(苯并15-冠-5)在水-氯仿体系中进行萃取,测量了分配比D和萃取平衡常数K,发现后者的K值均大于前者。双冠醚F_2对K~+的萃取能力最强,选择性最佳。     

酶分子在试管内的定向进化及其在手性有机物合成中的应用

本文扼要介绍了当今改进酶分子性能的有效手段———分子定向进化技术的基本方法如易错PCR和DNA洗牌,以及派生的一些新技术的原理与进展,并列举了在手性有机物合成中一些成功的实例,为该领域的研究与应用提供了一些新的信息。     

Intramolecular hydrogen bonds and hydrogen-bonded systems in di-Schiff bases of 4-methyl-isophthalaldehyde with 4-substituted anilines

Three di-Schiff bases of 2-hydroxy-5-methyl-isophthalaldehyde with 4-R-anilines (R=H, CH₃, OCH₃) and their 1:1 complexes with HClO₄ were studied by FT-IR, ¹H, and ¹³C NMR spectroscopy in acetonitrile and [²H₃]acetonitrile solutions, respectively. In di-Schiff bases intramolecular OH…N hydrogen bonds have been detected; however, they show no proton polarizability. Hydrogen-bonded systems with fast proton fluctuation and large proton polarizability have been found in the 1:1 complexes of di-Schiff bases with HClO₄.