Observed rotation enantiomers, chiral

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]. 

Chirality in the world of observables is characterized by pseudoscalar properties—properties that remain invariant under proper rotation but change sign under improper rotation. Enantiomers and, in general, enan-tiomorphous molecules, have identical scalar properties, such as melting points or dipole moments, and pseudoscalar properties that are identical in... 

Chemists have determined the absolute configurations of many chiral compounds since 1951, when X-ray crystallography was first used to find the orientation of atoms in space. Before 1951, there was no way to link the stereochemical drawings with the actual enantiomers and their observed rotations. No absolute configurations were known. It was possible, howevCT, to correlate the configuration of one compound with another and to show that two compounds had the same or opposite configurations. When we convert one compound into another using a reaction that does not break bonds at the asymmetric carbon atom, we know that the product must have the... 

If a sample of a pure substance that has two or more chirality centers has an observed rotation of zero, it could be a racemate. Could it possibly be a pure stereoisomer Could it possibly be a pure enantiomer ... 

Fill a 0.5-dm polarimeter cell with your chiral hydroxyester (about 2 mL required). You may need to combine your product with material obtained by one other student in order to have enough material to fill the cell. Determine the observed optical rotation for the chiral material. Your instructor will show you how to use the polarimeter. Calculate the specific rotation for your sample using the equation provided in Technique 23. The concentration value, c, in the equation is 1.02 g/mL. Using the published value for the specific rotation of ethyl (S)-(-l-)-3-hydroxybutanoate of [ d ] = +43.5°, calculafe fhe optical purity (enantiomeric excess) for your sample (see Technique 23, Section 23.5). Report the observed rotation, the calculated specific rotation, the optical purity (enantiomeric excess), and the percentages of each of the enantiomers to the instructor. How do the percentages of each of the enantiomers calculated from the polarimeter measurement compare to the values obtained from chiral gas chromatography ... 

A polarimeter will be used to measure the observed rotation, a, of the resolved amine sample. From this value, you will calculate the specific rotation [a]p and the optical purity (enantiomeric excess) of the amine. You will then calculate the percentages of each of the enantiomers present in the resolved sample. The (S)-a-phenylethylamine predominates in the sample. An optional chiral gas chromatographic method may be used to directly determine the percentages of each of the enantiomers in the sample. 

We have covered the way in which enantiomers differ from each other physically They rotate the plane of plane-polarized light in opposite directions. Before we go on to talk about how enantiomers differ in their chemical reactivity, let s take a little time to say something about the phenomenon of optical activity. How does a collection of atoms (a molecule) interact with a wave phenomenon (light), and how does the property of chirality (handedness) induce the observed rotation ... 

Twice before we have seen molecules that for different reasons give no observable rotation of plane-polarized light. Neither achiral molecules nor racemic mixtures of enantiomers can induce optical rotation. A racemic mixture of chiral... 

Optically Inactive Chiral Compounds. Although chirality is a necessary prerequisite for optical activity, chiral compounds are not necessarily optically active. With an equal mixture of two enantiomers, no net optical rotation is observed. Such a mixture of enantiomers is said to be racemic and is designated as ( ) and not as dl. Racemic mixtures usually have melting points higher than the melting point of either pure enantiomer. 

It is well known that spontaneous resolution of a racemate may occur upon crystallization if a chiral molecule crystallizes as a conglomerate. With regard to sulphoxides, this phenomenon was observed for the first time in the case of methyl p-tolyl sulphoxide269. The optical rotation of a partially resolved sulphoxide (via /J-cyclodextrin inclusion complexes) was found to increase from [a]589 = + 11.5° (e.e. 8.1%) to [a]589 = +100.8 (e.e. 71.5%) after four fractional crystallizations from light petroleum ether. Later on, few optically active ketosulphoxides of low optical purity were converted into the pure enantiomers by fractional crystallization from ethyl ether-hexane270. This resolution by crystallization was also successful for racemic benzyl p-tolyl sulphoxide and t-butyl phenyl sulphoxide271. 

Most of the physical properties (e.g., boiling and melting point, density, refractive index, etc.) of two enantiomers are identical. Importantly, however, the two enantiomers interact differently with polarized light. When plane polarized light interacts with a sample of chiral molecules, there is a measurable net rotation of the plane of polarization. Such molecules are said to be optically active. If the chiral compound causes the plane of polarization to rotate in a clockwise (positive) direction as viewed by an observer facing the beam, the compound is said to be dextrorotatory. An anticlockwise (negative) rotation is caused by a levorotatory compound. Dextrorotatory chiral compounds are often given the label d or ( + ) while levorotatory compounds are denoted by l or (—). 

A young Louis Pasteur observed that many salts of tartaric acid formed chiral crystals (which he knew was related to their ability to rotate the plane of polarization of plane-polarized light). He succeeded in solving the mystery of racemic acid when he found that the sodium ammonium salt of racemic acid could be crystallized to produce a crystal conglomerate. After physical separation of the macroscopic enantiomers with a dissecting needle, Pasteur... 

The experimentally observable phenomenon of optical activity is usually considered in the context of variation of molecular chirality arising from a particular stereochemical configuration at a particular atom such that the molecule has no improper rotation S axis. Molecules with opposite chirality configurations are enantiomers and show oppositely signed optical activity. Molecules differing only in conformation are called conformers or rotational isomers. In most cases, the difference in energy between rotational isomeric states is very small, such that at ambient temperature all are populated and no optical activity results. However, if one particular conformer is stabilized, for example, by restriction of rotation about a bond, the molecule can become chiral, and thus optically active. 

Tius and co-workers elegantly applied a variant of the Nazarov reaction to the preparation of cyclopentenone prostaglandins (Scheme 19.39) [46]. Moreover, it was demonstrated that the chirality of non-racemic allenes is transferred to an sp3-hybridized carbon atom. Preparation of allenic morpholinoamide 214 and resolution of the enantiomers by chiral HPLC provided (-)- and (+)-214. Compound (-)-214 was exposed to the vinyllithium species 215 to afford a presumed intermediate which was not observed but spontaneously cyclized to give (+)- and (—)-216 as a 5 1 mixture. Compound (+)-216 was obtained with an 84% transfer of chiral information and (-)-216 was obtained in 64% ee. The lower enantiomeric excess of (—)-216 indicates that some Z to E isomerization took place. This was validated by the conversion of 216 to 217, where the absolute configuration was established. The stereochemical outcome of this reaction has been explained by conrotatory cyclization of 218 in which the distal group on the allene rotates away from the alkene to give 216. 

Molecular asymmetry, chirality and enantiomers The observation of Louis Pasteur (1848) that crystals of certain compounds exist in the form of mirror Images laid the foundation of modem stereochemistry. He demonstrated that aqueous solutions of both types of crystals showed optical rotation, equal in magnitude (for solution of equal concentration) but opposite in direction. He believed that this difference in... 

As Louis Pasteur first observed (Box 1-2), enantiomers have nearly identical chemical properties but differ in a characteristic physical property, their interaction with plane-polarized light. In separate solutions, two enantiomers rotate the plane of plane-polarized light in opposite directions, but an equimolar solution of the two enantiomers (a racemic mixture) shows no optical rotation. Compounds without chiral centers do not rotate the plane of plane-polarized light. 

The first successful experiments were reported by Schwab [16] Cu, Ni and Pt on quartz HI were used to dehydrogenate racemic 2-butanol 23. At low conversions, a measurable optical rotation of the reaction solution indicated that one enantiomer of 23 had reacted preferentially (eeright-handed quartz gave the opposite optical rotation it was deduced that the chiral arrangement of the crystal was indeed responsible for this kinetic resolution (for a review see [8]). Later, natural fibres like silk fibroin H5 (Akabori [21]), polysaccharides H8 (Balandin [23]) and cellulose H12 (Harada [29]) were employed as chiral carriers or as protective polymer for several metals. With the exception of Pd/silk fibroin HS, where ee s up to 66% were reported, the optical yields observed for catalysts from natural or synthetic (H8, Hll. H13) chiral supports were very low and it was later found that the results observed with HS were not reproducible [4],... 

The chirality observed in this kind of substituted allene is a consequence of dissymmetry resulting from restricted rotation about the double bonds, not because of a tetrahedral atom carrying four different groups. Restricted rotation occurs in many other kinds of compounds and a few examples are shown in Table 13-3, which includes trans-cycloalkenes (Section 12-7), cycloalkyli-denes, spiranes, and ort/zo-substituted biphenyl compounds. To have enantiomers, the structure must not have a plane or center of symmetry (Section 5-5). 

Chow and Mak came to a similar conclusion on investigating the chiroptical properties of dendrimers containing enantiomerically pure threitol building blocks obtained from tartaric acid as spacers between the achiral phloroglucin branching units (see Fig. 4.73) [27]. They found that the chiral spacers in the dendrimer scaffold do not influence one another and contribute additively to the overall rotation. Moreover, they also observed that on introduction of both enantiomers one (R,R)-threitol unit precisely compensated the rotational contribution of one (S,S)-threitol unit, provided that the enantiomeric building blocks were located at equivalent positions within the dendrimer scaffold. However, CD-spectroscopic data revealed that the contribution of the exterior threitol units to the total rotation must be slightly different from that of the interior units. 

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