Racemic mixtures formation

In the second scenario, target products and impurities are present in similar amounts. The separation of racemic mixtures exemplifies this scenario. The problem of racemic mixture formation often occurs during chemical synthesis, where 50% of the mixture consists of the wanted enantiomer (eutomer) and 50% is the unwanted enantiomer (distomer). In this case competitive adsorption and the elution order of the enantiomers are of special interest (Section 4.3.4). 

It IS a general principle that optically active products cannot be formed when opti cally inactive substrates react with optically inactive reagents This principle holds irre spective of whether the addition is syn or anti concerted or stepwise No matter how many steps are involved m a reaction if the reactants are achiral formation of one enan tiomer is just as likely as the other and a racemic mixture results... 

As a general rule, formation of a new chirality center by reaction betweer two achiral reactants always leads to a racemic mixture of enantiomeri<... 

A different situation arises when one considers a stereospecific catalyst which is endowed with optical activity and which favors therefore a specific configuration. Such a catalyst, if highly stereospecific, should form polymers, for example of all d configuration with an occasional inclusion here and there of l units. Of course if a racemic mixture of such a catalyst is used, then formation of a racemic mixture of polymers is expected, each polymeric molecule having an all d configuration incrusted with l units or an all l configuration incrusted with d units. 

The steroid ring structure is complex and contains many chiral carbons (for example at positions 5, 8, 9,10,13,14 and 17) thus many optical isomers are possible. (The actual number of optical isomers is given by 2" where n = the number of chiral carbons). From your knowledge of biochemistry you should have realised that only one of these optical isomers is likely to be biologically active. Synthesis of such a complex chemical structure to produce a single isomeric form is extremely difficult, especially when it is realised that many chemical reactions lead to the formation of racemic mixtures. Thus, for complete chemical synthesis, we must anticipate that... 

Racemic mixtures of sulfoxides have often been separated completely or partially into the enantiomers. Various resolution techniques have been used, but the most important method has been via diastereomeric salt formation. Recently, resolution via complex formation between sulfoxides and homochiral compounds has been demonstrated and will likely prove of increasing importance as a method of separating enantiomers. Preparative liquid chromatography on chiral columns may also prove increasingly important it already is very useful on an analytical scale for the determination of enantiomeric purity. 

Thus the product in such cases can exist as two pairs of enantiomers. In a di-astereoselective process, one of the two pairs is formed exclusively or predominantly as a racemic mixture. Many such examples have been reported. In many of these cases, both the enolate and substrate can exist as (Z) or (E) isomers. With enolates derived from ketones or carboxylic esters, (E) enolates gave the syn pair of enantiomers (p. 146), while (Z) enolates gave the anti pair. Addition of chiral additives to the reaction, such as proline derivatives, or (—)-sparteine lead to product formation with good-to-excellent asynunetric induction. Ultrasound has also been used to promote asymmetric Michael reactions. Intramolecular versions of Michael addition are well known. ... 

Figure 4.8 Coupling with irreversible step synthesis of D-amino acids from racemic mixture applying a batch process coupling the reaction to the formation of the gaseous side-product C02...

Amino acid formation in the Urey-Miller experiment and almost certainly in the prebiotic environment is via the Stecker synthesis shown in Figure 8.3. This reaction mechanism shows that the amino acids were not formed in the discharge itself but by reactions in the condensed water reservoir. Both HCN and HCO are formed from the bond-breaking reactions of N2 and H2O in a plasma, which then react with NH3 in solution. The C=0 group in formaldehyde or other aldehydes is replaced by to form NH and this undergoes a reaction with HCN to form the cyano amino compound that hydrates to the acid. The Strecker synthesis does not provide stereo-control over the carbon centre and must result in racemic mixtures of amino acids. There is no room for homochirality in this pathway. 

CAS 4368-28-9 39920-04-2 (Racemic mixture) 629653-73-2 (Acetate salt) 18660-81-6 (Citrate salt) 17522-62-2 (Formate salt) 4664-41-9 (Hydrobromide salt) 4664-40-8 (Picrate salt) 129497-92-3 (Trifluoroacetate salt)... 

Syntheses of naphthyridone derivatives follow the same procedures as those of quinolones, except that substituted 2-aminopyridines (Gould-Jacobs modification) or substituted nicotinic ester/nicotinoyl chloride are used instead of anilines or o-halobenzoic acid derivatives. Most of the recently introduced quinolone antibacterials possess bicyclic or chiral amino moieties at the C-7 position, which result in the formation of enantiomeric mixtures. In general, one of the enantiomers is the active isomer, therefore the stereospecific synthesis and enantiomeric purity of these amino moieties before proceeding to the final step of nucleophilic substitution at the C-7 position of quinolone is of prime importance. The enantiomeric purity of other quinolones such as ofloxacin (a racemic mixture) plays a major role in the improvement of the antibacterial efficacy and pharmacokinetics of these enan-... 

Similarly the addition of bromine to maleic acid giving a racemic mixture of dibromosuccinic acid is again a trans addition. Here also there is first the formation of a bridged (or a non-classical) carbocation followed by the attack of the bromide ion. The various steps are as follows ... 

For diene ligands which are prochiral, complexation results in the formation of a racemic mixture. Resolution of this racemic mixture has been accomplished via either classical methods102, chromatographic separation on chiral stationary phases103 or kinetic resolution104. For certain acyclic or cyclic dienes possessing a pendent chiral center(s)... 

SRURC is such an interesting example of the facile formation of chiral induction from racemic mixtures in the absence of any external symmetry-breaking agent that it deserves special attention. One of the best studied examples is the crystallization of bromofluoro-l,4-benzodiazepinooxazole (Fig. 11.3), which possesses a single asymmetric carbon atom at C14 and a potentially asymmetric bridgehead nitrogen atom at N4. 

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