手性有机磷化合物液相拆分的研究进展

 综述了近年来手性有机磷化合物液相拆分的研究进展。对间接拆分和直接拆分法,特别是各类手性固定相法在拆分有机磷化合物中的应用作了介绍,探讨了相应的拆分机理。85篇。     

化学拆分的新方法研究

主要介绍了近年来发展起来的两种化学拆分新方法,包括拆分和组合拆分;并简要论述了化学拆分中的手性识别现象,以及化学拆分方法在手性药物制备中的应用。     

毛细管电泳在手性氨基酸拆分中的研究进展

毛细管电泳(capillary electrophoresis,CE)作为一种强有力的手性分离技术,由于操作简单、试剂消耗少及柱效高等优点,受到广泛关注,是近年来手性分离领域的研究热点.氨基酸是组成蛋白质的基本单元,且大多数氨基酸具有手性中心,手性氨基酸是生命体系的一个重要特征.具有手性中心的氨基酸,其对映体间的生物活性往往存在着较大的差异,因此,氨基酸的手性拆分对了解人体及动物生命活动起着举足轻重的作用.主要总结了近5年来毛细管电泳的3种分离模式(毛细管区带电泳、胶束电动毛细管色谱、毛细管电色谱)在氨基酸手性拆分中的发展和应用.     

叔醇的动力学拆分研究进展

手性叔醇结构广泛存在于生物活性物质、天然产物和药物分子中,实现其高效不对称催化合成具有重要意义.消旋醇的动力学拆分是一种合成高光学纯度手性醇的重要方法,然而由于叔醇α-碳上带三个不同的非氢取代基团,手性识别难度较大,因而发展高效且具有广泛底物适用性的叔醇动力学拆分方法具有较大的挑战.尽管如此,近年来非酶催化的叔醇的动力学拆分领域取得了快速的发展,一些新颖的不对称催化反应、催化体系被成功应用于叔醇的动力学拆分反应中.对叔醇动力学拆分反应进行了系统总结,分类介绍了这些反应的底物适用性、特点、机理以及局限等,并对该领域的未来发展进行展望.     

手性化合物的动态动力学拆分研究进展

获得光学纯手性化合物已成为精细化学品和制药行业的重要目标,外消旋体的拆分是合成光学纯手性化合物最主要的途径之一[1],其中动力学拆分是常用的方法.然而经典的动力学拆分方法的缺点是最大理论产率仅为50%.     

一种新的手性拆分方法-包结拆分

综述了手性包结拆分方法在拆分外消旋化合物中的应用,并讨论了包结拆分中的手性识别原理。     

手性药物的毛细管电泳拆分环糊精系统

以本实验室工作为背景，结合国内外最新文献，对环糊精系统分离手性化合物的包合机理，拆分外部条件及其应用进行了详细介绍与评述。     

药物的手性拆分

手性药物在医学应用中具有广阔的应用前景。本文介绍了常用药物的手性拆分方法,包括机械拆分法、经典成盐拆分法、色谱拆分方法及酶拆分法等的拆分原理,并对它们的应用领域及优缺点进行了比较分析。以期对新药的手性拆分及现有药物的拆分优化提供一般的理论参考。     

手性亚砜类化合物的包结拆分

本文简要综述了手性亚砜类化合物的包结拆分研究,介绍了吡啶亚砜类化合物（包括苯并咪唑类抗胃溃疡药物）的包结拆分研究的最近进展。     

一种新的手性拆分方法-包结拆分

综述了手性包结拆分方法在拆分外消旋化合物中的应用,并讨论了包结拆分中的手性识别原理。     

含氟手征性分子的拆分

本文总结了手征性氟代醇、酸、胺、联苯类,由于分子过分拥挤而造成的不对称化合物及手征性全氟化合物的拆分。阐述了这项工作在生物化学、有机合成、有机分析以及有机反应机理的研究等方面的特殊意义。     

The Dutch Resolution variant of the classical resolution of racemates by formation of diastereomeric salts: family behaviour in nucleation inhibition

The resolution of racemates through their diastereomeric salts can be positively affected by the addition of small amounts of suitable nucleation inhibitors. This discovery is a logical extension of "Dutch Resolution", in which equimolar amounts of resolving agents that are members of the same family (i.e., structurally related) are used. We conducted a systematic search for nucleation inhibitors of the resolving agent 1-phenylethylamine. A wide range of amines that bear possible family resemblances to 1-phenylethylamine was investigated. It was found that (R)-1-phenylbutylamine is a good inhibitor of (R)-1-phenylethylamine. Results of turbidity measurements showed that, for the model case of mandelic acid resolution, the chief effect of this inhibitor was to widen the metastable zone for the more soluble diastereomer. This observation is in accordance with previous experience. Further scouting for possible family members revealed a wide variation in the effectiveness of inhibitors, dependent on their structure. By far the most effective inhibitors are bifunctional 1-phenylethylamine and/or 1-phenylbutylamine analogues. The effect of racemic inhibitors was found to approach that of enantiomerically pure inhibitors of the same absolute configuration of the 1-phenylethylamine used for resolution. The most effective inhibitors were tested for the resolution of a structural variety of racemates, and were shown to be broadly applicable.     

A Racemic and Enantiopure Unsymmetric Diiron(III) Complex with a Chiral o‐Carborane‐Based Pyridylalcohol Ligand: Combined Chiroptical,Magnetic, and Nonlinear Optical Properties

The design of molecule‐based systems combining magnetic, chiroptical and second‐order optical nonlinear properties is still very rare. We report an unusually unsymmetric diiron(III) complex 1 , in which three bulky chiral carboranylpyridinealkoxide ligands ( o CB hmp^?) bridge both metal ions and the complex shows the above‐mentioned properties. The introduction of o‐carborane into the 2‐(hydroxymethyl)pyridine (hmpH) architecture significantly alters the coordination of the simple or aryl‐substituted 2‐hmpH. The unusual architecture observed in 1 seems to be triggered by the poor nucleophilicity of our alkoxide ligand ( o CB hmp^?). A very rare case of spontaneous resolution takes place on precipitation or exposure to solvent vapor for the bulk compound, as confirmed by a combination of single‐crystal and powder X‐ray diffraction, second‐harmonic generation, and circular dichroism. The corresponding enantiopure complexes (+) 1 and (?) 1 have also been synthesized and fully characterized. This research provides a new building block with unique geometry and electronics to construct coordination complexes with multifunctional properties.     

Catalytic Kinetic Resolution of Biaryl Compounds

Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds.     

Resolution of seven-coordinate complexes

The crystal structures of [Pr(dbm)3H2O] (1), [Sm(dbm)3H2O] (2), and [Er(dbm)3H2O] (3) have been determined (dbm=dibenzoylmethane). They display seven-coordinate propeller-shaped molecules, which are chiral and crystallize as conglomerates in space group R3. Analysis of the crystal structures reveals supramolecular interactions, including formation of a quadruple helix, which explain how stereochemical information can be transferred between stacks of molecules. A method to quantify the ee in bulk samples of stereochemically labile compounds by using solid-state CD spectroscopy is described. Using this method, it has been shown that compounds 1-3 undergo total spontaneous resolution directly after synthesis, forming a microcrystalline reaction product that is essentially enantiopure. The resolution of bulk quantities of seven-coordinate complexes (without chiral or polydentate ligands) is thus reported for the first time. Because the crystallization starts without seeding, the overall preparation may be regarded as absolute asymmetric synthesis.     

Practical Tactics in Resolution of Racemates via Diastereomeric Salt Formation

A practical tactics in the classical resolutions was illustrated for affording the desired isomers in maximum yields. According to the practical tactics resolution of racemic ethyl nipecotate, Corey lactone and huperzine A intermediate was successfully practiced. The basis of this practicability is the well-known Marckwald principle.     

Enantiopure Functional Molecular Motors Obtained by a Switchable Chiral‐Resolution Process

Molecular switches, rotors, and motors play an important role in the development of nano‐machines and devices, as well as responsive and adaptive functional materials. For unidirectional rotors based on chiral overcrowded alkenes, their stereochemical homogeneity is of crucial importance. Herein, a method to obtain new and functionalizable overcrowded alkenes in enantiopure form is presented. The procedure involves a short synthesis of three steps and a solvent‐switchable chiral resolution by using a readily available resolving agent. X‐ray crystallography revealed the mode of binding of the motor with the resolving agent, as well as the absolute configuration of the motor. ¹H NMR and UV/Vis spectroscopy techniques were used to determine the dynamic behavior of this molecular motor. This method provides rapid access to ample amounts of enantiopure molecular motors, which will greatly facilitate the further development of responsive molecular systems based on chiral overcrowded alkenes.