Chirality basic principles

For the separation of amino acids, the applicability of this principle has been explored. For the separation of racemic phenylalanine, an amphiphilic amino acid derivative, 1-5-cholesteryl glutamate (14) has been used as a chiral co-surfactant in micelles of the nonionic surfactant Serdox NNP 10. Copper(II) ions are added for the formation of ternary complexes between phenylalanine and the amino acid cosurfactant. The basis for the separation is the difference in stability between the ternary complexes formed with d- or 1-phenylalanine, respectively. The basic principle of this process is shown in Fig. 5-17 [72]. 

Capillary electrochromatography-mass spectrometry (CE-MS), 4 641 Capillary electrodes, 14 27 Capillary electrophoresis (CE), 4 602-603, 631-633 6 385 9 751-752 antibody based columns with, 6 402 chiral additives, 6 77-79 applications, 4 641 basic principles, 4 606-609 detectors, 4 634-635 for DNA analysis, 4 636-637 flow profiles generated, 4 608 instrumentation, 4 633 as microfluidic assay technique,... 

The basic principles of the mechanism of this Lewis-base-catalyzed aldol reaction have already been described in Section 6.2.1.1. With regard to the course of the enantio- and diastereoselective formation of aldol adducts with two stereogenic centers, it is proposed that synthesis of anti-products proceeds via a chair-like transition structure. A distinctive feature of the cationic transition state complex is a hexacoordinated silicon atom bearing two chiral phosphoramide molecules as ligands (Scheme 6.30). 

Asymmetric catalytic addition of dialkylphosphites to a C=0 double bond is a powerful method, and probably the most general and widely applied, for formation of optically active a-hydroxy phosphonates [258], The basic principle of this reaction is shown in Scheme 6.108. Several types of catalyst have been found to be useful. The transition-metal-catalyzed asymmetric hydrophosphonylation using chiral titanium or lanthanoid complexes was developed by several groups [259, 260], The most efficient type of chiral catalyst so far is a heterobimetallic complex consisting... 

The basic principles of asymmetric synthesis have been discussed in a number of recent reviews (2,3). The heart of an asymmetric synthesis is a reaction in which an achiral unit in an ensemble of substrate molecules is converted into a chiral unit in such a manner that the stereoisomeric products are obtained in unequal amounts. For almost all cases this is equivalent to the statement that in an asymmetric reaction a prochiral unit is converted into a chiral unit. 

A recent discovery that has significantly extended the scope of asymmetric catalytic reactions for practical applications is the metal-complex-catalyzed hydrolysis of a racemic mixture of epoxides. The basic principle behind this is kinetic resolution. In practice this means that under a given set of conditions the two enantiomers of the racemic mixture undergo hydrolysis at different rates. The different rates of reactions are presumably caused by the diastereo-meric interaction between the chiral metal catalyst and the two enantiomers of the epoxide. Diastereomeric intermediates and/or transition states that differ in the energies of activation are presumably generated. The result is the formation of the product, a diol, with high enantioselectivity. One of the enantiomers of... 

Although the basic principle and procedure of diastereomeric resolution are not difficult to understand, the chiral discrimination mechanism involved in the selective crystallization of one diastereomer from the mixture is very complicated. The chiral discrimination mechanism for diastereomeric resolution changes in accord with the resolving system, since not only the properties of diastereomeric crystals but also the conditions for crystallization strongly influence the chiral discrimination mechanism. In particular, the polymorphism of crystal, the severe solvent effect on solubility, and the kinetic factor for crystal growth are still not perfectly understood regarding this chiral discrimination phenomenon. The study is therefore limited in its investigation of the chiral discrimination mechanism for the diastereomeric resolution, as the mechanism involves both the crystal and solution properties of diastereomers.7... 

Ion Chromatography, edited by James G. Tarter 38. Chromatographic Theory and Basic Principles, edited by Jan Ake Jonsson 39. Field-Flow Fractionation Analysis of Macromolecules and Particles, Josef Janca 40. Chromatographic Chiral Separations, edited by Morris Zief and Laura J. Crane 41. Quantitative Analysis by Gas Chromatography, Second Edition, Revised and Expanded, Josef... 

The lack of resolution by which mechanism the osmylation proceeds has resulted in two models to rationalize the face selectivity of the AD reaction. The commonality of these two predictive models resides in the basic principle that a chiral binding pocket is formed from the ligand s aromatic groups. However, the shape and location of this pocket in the complex is not identical. 

Sharpless asymmetric epoxidation is the first example of a reaction where an achiral precursor is converted to a chiral substrate with high enantioselectivity. This discovery triggered a flurry of activity, applying the basic principles of asymmetric epoxidation to a variety of other reactions. Sharpless asymmetric epoxidation is very important in the synthesis of natural products since this reaction offers an asymmetric route to many important synthons. One example is the conversion of 224 to 225, in 95% yield (> 15 1 de), in Meyer s synthesis of disorazole Ci, where MS indicates the use of molecular sieves.321 In a second example, taken... 

Reduction of ketones with borane. The basic principle for employing chiral... 

Chiral separation or sorption is another important technique in chirotechnology. In fact, due to the high cost of chiral catalysts, industries generally prefer chiral separation over asymmetric catalysis to obtain optically pure compounds. As in asymmetric heterogeneous catalysis, a chiral selector (a chiral molecule in optically pure form) can be immobilized on a solid support to make a chiral stationary phase (CSP) of use in direct chiral separation. The basic principle of chiral separation is that the chiral selector interacts differently with the enantiomers of a racemic or enantioenriched mixture to form transient diastereoisomeric species of different stability, and this fine distinction leads to the separation of enantiomers during elution. This topic has also produced a huge number of papers and the readers are referred to the previous reviews for more knowledge on this field [70-73]. 

We begin our treatment with a brief introduction to the basic principles of chirality and then describe its use as a powerful tool in the economic manufacture of a variety of stereospecific chemicals (thus all but eliminating the untoward effects of admixture with their stereoisomers). 

Chiral Gas Chromatography Applications The Basic Principles of Chiral Selectivity Test Mixtures... 

Synthetic methods for enantiomers in a drug discovery programme differ appreciably from those used in their manufacture but the same basic principles are useful in both, for example, resolution by physical, chemical, or biocatalytic means, asymmetric synthesis, or use of the chirality pool. Generally, the method of choice ultimately used in manufacture of a pharmaceutical will be quite different from that first used to obtain the single-enantiomer material in a drug-discovery programme. 

Interpretation of CD spectra may be conducted based solely on basic principles such as (7), exciton chirality method, and ICD phenomenon. However, when the analysis of CD... 

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