Chiral separation Chirality

Chiral liquid crystals Chiral recognition Chiral separation Chiral separations Chiral shift reagents... 

P. A. (2000). Generic approach to chiral separations chiral capillary electrophoresis with ternary cyclodextrin mixtures. /. Microcol. Sep. 12, 568 — 576. 

Capillary tubing - [IRACE AND RESIDUE ANALYSIS] (Vol 24) -m chiral separations [CHIRAL SEPARATIONS] (Supplement) -m trace analysis [IRACE AND RESIDUE ANALYSIS] (Vol 24) -of vitreous silica [SILICA - VITREOUS SILICA] (Vol 21)... 

CHIRAL SEPARATIONS. Chiral separations are concerned with separating molecules that can exist as nnnsuperimposyhle mirror images Examples of these types of molecules, called enantiomers or optical isomers. are illustrated in Figure I. Although chirality is often associated with compounds containing a tetrahedral carbon w ith four different substituents, other atoms, such as phosphorus or sulfur, may also be chiral. In addition,... 

Recently developed techniques for chiral separation chiral membranes... 

An example of a chiral compound is lactic acid. Two different forms of lactic acid that are mirror images of each other can be defined (Figure 2-69). These two different molecules are called enantiomers. They can be separated, isolated, and characterized experimentally. They are different chemical entities, and some of their properties arc different (c.g., their optical rotation),... 

The Cahn-Ingold-Prelog (CIP) rules stand as the official way to specify chirahty of molecular structures [35, 36] (see also Section 2.8), but can we measure the chirality of a chiral molecule. Can one say that one structure is more chiral than another. These questions are associated in a chemist s mind with some of the experimentally observed properties of chiral compounds. For example, the racemic mixture of one pail of specific enantiomers may be more clearly separated in a given chiral chromatographic system than the racemic mixture of another compound. Or, the difference in pharmacological properties for a particular pair of enantiomers may be greater than for another pair. Or, one chiral compound may rotate the plane of polarized light more than another. Several theoretical quantitative measures of chirality have been developed and have been reviewed elsewhere [37-40]. 

Application of the CCM to small sets (n < 6) of enzyme inhibitors revealed correlations between the inhibitory activity and the chirality measure of the inhibitors, calculated by Eq. (26) for the entire structure or for the substructure that interacts with the enzyme (pharmacophore) [41], This was done for arylammonium inhibitors of trypsin, Di-dopamine receptor inhibitors, and organophosphate inhibitors of trypsin, acetylcholine esterase, and butyrylcholine esterase. Because the CCM values are equal for opposite enantiomers, the method had to be applied separately to the two families of enantiomers (R- and S-enantiomers). 

Twenty-eight chiral compounds were separated from their enantiomers by HPLC on a teicoplanin chiral stationary phase. Figure 8-12 shows some of the structures contained in the data set. This is a very complex stationary phase and modeling of the possible interactions with the analytes is impracticable. In such a situation, learning from known examples seemed more appropriate, and the chirality code looked quite appealing for representing such data. 

Figure 8-12. Examples of las eluted enantiomers In a chromatographic separation on chiral HPLC with teicoplanin stationary-phase.

Chirality (handedness) is older than life on tliis planet. Still it was not until 1848 when Pasteur manually separated enantiomeric crystals that chirality in chemistry was first appreciated ". The independent work of Van t Hoff and Le Bel revealed the molecirlar origin behind this phenomenon. 

Clearly, there is a need for techniques which provide access to enantiomerically pure compounds. There are a number of methods by which this goal can be achieved . One can start from naturally occurring enantiomerically pure compounds (the chiral pool). Alternatively, racemic mixtures can be separated via kinetic resolutions or via conversion into diastereomers which can be separated by crystallisation. Finally, enantiomerically pure compounds can be obtained through asymmetric synthesis. One possibility is the use of chiral auxiliaries derived from the chiral pool. The most elegant metliod, however, is enantioselective catalysis. In this method only a catalytic quantity of enantiomerically pure material suffices to convert achiral starting materials into, ideally, enantiomerically pure products. This approach has found application in a large number of organic... 

Sharpless epoxidations can also be used to separate enantiomers of chiral allylic alcohols by kinetic resolution (V.S. Martin, 1981 K.B. Sharpless, 1983 B). In this procedure the epoxidation of the allylic alcohol is stopped at 50% conversion, and the desired alcohol is either enriched in the epoxide fraction or in the non-reacted allylic alcohol fraction. Examples are given in section 4.8.3. 

The 1,6-difunctional hydroxyketone given below contains an octyl chain at the keto group and two chiral centers at C-2 and C-3 (G. Magnusson, 1977). In the first step of the antithesis of this molecule it is best to disconnect the octyl chain and to transform the chiral residue into a cyclic synthon simultaneously. Since we know that ketones can be produced from add derivatives by alkylation (see p. 45ff,), an obvious precursor would be a seven-membered lactone ring, which is opened in synthesis by octyl anion at low temperature. The lactone in turn can be transformed into cis-2,3-dimethyicyclohexanone, which is available by FGI from (2,3-cis)-2,3-dimethylcyclohexanol. The latter can be separated from the commercial ds-trans mixture, e.g. by distillation or chromatography. 

This method is widely used for the resolution of chiral amines and carboxylic acids Analogous methods based on the formation and separation of diastereomers have been developed for other functional groups the precise approach depends on the kind of chem ical reactivity associated with the functional groups present m the molecule... 

A few GLC stationary phases rely on chemical selectivity. The most notable are stationary phases containing chiral functional groups, which can be used for separating enantiomers. ... 

This experiment introduces the use of a chiral column (a 3-cyclodextrin-bonded Cjg column) to separate the beta-blocker drugs Inderal LA (S-propranolol and... 

In this experiment the enantiomers of cyclobarbital and thiopental, and phenobarbital are separated using MEKC with cyclodextran as a chiral selector. By adjusting the pH of the buffer solution and the concentration and type of cyclodextran, students are able to find conditions in which the enantiomers of cyclobarbital and thiopental are resolved. 

In Section 4.2.1 it will be pointed out that hydrogen peroxide (Figure 4.1 la) has only one symmetry element, a C2 axis, and is therefore a chiral molecule although the enantiomers have never been separated. The complex ion [Co(ethylenediamine)3], discussed in Section 4.2.4 and shown in Figure 4.11(f), is also chiral, having only a C3 axis and three C2 axes. 

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