Chiral molecules enantiomers

Drawing a chiral molecule (enantiomer) On a plane paper, chiral molecules can be drawn using wedge bonds. There are also a few other methods that use horizontal bonds representing bonds pointing out of the paper and vertical bonds pointing into the paper. Some examples are given below. 

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]. 

The difference m odor between (R) and (S) carvone results from their different behavior toward receptor sites m the nose It is believed that volatile molecules occupy only those odor receptors that have the proper shape to accommodate them Because the receptor sites are themselves chiral one enantiomer may fit one kind of receptor while the other enantiomer fits a different kind An analogy that can be drawn is to hands and gloves Your left hand and your right hand are enantiomers You can place your left hand into a left glove but not into a right one The receptor (the glove) can accommodate one enantiomer of a chiral object (your hand) but not the other... 

The term chiral recognition refers to a process m which some chiral receptor or reagent interacts selectively with one of the enantiomers of a chiral molecule Very high levels of chiral recognition are common m biological processes (—) Nicotine for exam pie IS much more toxic than (+) nicotine and (+) adrenaline is more active than (—) adrenaline m constricting blood vessels (—) Thyroxine an ammo acid of the thyroid gland that speeds up metabolism is one of the most widely used of all prescription... 

Section 7 2 The most common kind of chiral molecule contains a carbon atom that bears four different atoms or groups Such an atom is called a chirality center Table 7 2 shows the enantiomers of 2 chlorobutane C 2 is a chi rahty center m 2 chlorobutane... 

The enzyme is a single enantiomer of a chiral molecule and binds the coenzyme and substrate m such a way that hydride is transferred exclusively to the face of the carbonyl group that leads to (5) (+) lactic acid Reduction of pyruvic acid m the absence of an enzyme however say with sodium borohydride also gives lactic acid but as a racemic mixture containing equal quantities of the R and S enantiomers... 

Techniques for determining the absolute configuration of chiral molecules were not developed until the 1950s and so it was not possible for Eischer and his contemporaries to relate the sign of rotation of any substance to its absolute configuration A system evolved based on the arbitrary assumption later shown to be correct that the enantiomers... 

A chiral molecule is one which exists in two forms, known as enantiomers. Each of the enantiomers is optically active, which means that they can rotate the plane of plane-polarized light. The enantiomer that rotates the plane to the right (clockwise) has been called the d (or dextro) form and the one that rotates it to the left (anticlockwise) the I (or laevo) form. Nowadays, it is more usual to refer to the d and I forms as the ( + ) and (—) forms, respectively. 

Very often, a sample of a chiral molecule exists as an equimolar mixture of (+) and (—) enantiomers. Such a mixture will not rotate the plane of plane-polarized light and is called a... 

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. 

Although the usual absorption and scattering spectroscopies caimot distinguish enantiomers, certain techniques are sensitive to optical activity in chiral molecules. These include optical rotatory dispersion (ORD), the rotation by the sample of the plane of linearly polari2ed light, used in simple polarimeters and circular dichroism (CD), the differential absorption of circularly polari2ed light. 

Kinetic Resolutions. From a practical standpoint the principal difference between formation of a chiral molecule by kinetic resolution of a racemate and formation by asymmetric synthesis is that in the former case the maximum theoretical yield of the chiral product is 50% based on a racemic starting material. In the latter case a maximum yield of 100% is possible. If the reactivity of two enantiomers is substantially different the reaction virtually stops at 50% conversion, and enantiomericaHy pure substrate and product may be obtained ia close to 50% yield. Convenientiy, the enantiomeric purity of the substrate and the product depends strongly on the degree of conversion so that even ia those instances where reactivity of enantiomers is not substantially different, a high purity material may be obtained by sacrificing the overall yield. 

Synthetic chiral adsorbents are usually prepared by tethering a chiral molecule to a silica surface. The attachment to the silica is through alkylsiloxy bonds. A study which demonstrates the technique reports the resolution of a number of aromatic compoimds on a 1- to 8-g scale. The adsorbent is a silica that has been derivatized with a chiral reagent. Specifically, hydroxyl groups on the silica surface are covalently boimd to a derivative of f -phenylglycine. A medium-pressure chromatography apparatus is used. The racemic mixture is passed through the column, and, when resolution is successful, the separated enantiomers are isolated as completely resolved fiactions. Scheme 2.5 shows some other examples of chiral stationary phases. 

The minor images of bromochlorofluoromethane have the sane constitution. That is, the atoms are connected in the sane order. But they differ in the anangement of then-atoms in space they are stereoisomers. Stereoisomers that are related as an object and its nonsuperimposable minor image are classified as enantiomers. The word enantiomer describes a paiticulai- relationship between two objects. One cannot look at a single molecule in isolation and ask if it is an enantiomer any more than one can look at an individual human being and ask, Is that person a cousin Fuithennore, just as an object has one, and only one, minor image, a chiral molecule can have one, and only one, enantiomer. 

Let s return to bromochlorofluoromethane as a simple example of a chiral molecule. The two enantiomers of BrCIFCH are shown as ball-and-stick models, as wedge-and-dash drawings, and as Fischer projections in Figure 7.6. Fischer projections are always generated the same way the molecule is oriented so that the vertical bonds at the chirality center are directed away from you and the horizontal bonds point toward you. A projection of the bonds onto the page is a cross. The chirality center lies at the center of the cross but is not explicitly shown. 

Consider the stereochemical relationships between these flexible stereoisomers. A flexible molecule is chiral only if each of its conformers is chiral and if no two conformers are mirror images. Which, if any, of the stereoisomers are chiral Rexible chiral molecules are enantiomers only if each of their conformers are mirror-images. Which, if any, of the stereoisomers are enantiomers and which are diastereomers ... 

A chiral molecule need not contain a chiral center. Examine the two enantiomers of 2,3-pentadiene (A and B). 

Do you think it would be possible to resolve each chiral molecule into different enantiomers at room temperature Answer this question by calculating the half-hfe (x. ) of the pyramidal molecules at 298 K (use equation 1). 

Molecules that are not identical to their mirror images, and thus exist in two enantiomeric forms, are said to be chiral (ky-ral, from the Greek cheir, meaning "hand"). You can t take a chiral molecule and its enantiomer and place one on the other so that all atoms coincide. 

Although the different enantiomers of a chiral molecule have the same physical properties, they usually have different biological properties. For example, the (+) enantiomer of limonene has the odor of oranges, but the (-) enantiomer has the odor of pine trees. 

Figure 9.17 Imagine that a left hand interacts with a chiral object, much as a biological receptor interacts with a chiral molecule, (a) One enantiomer fits into the hand perfectly green thumb, red palm, and gray pinkie finger, with the blue substituent exposed. (b The other enantiomer, however, can t fit into the hand. When the green thumb and gray pinkie finger interact appropriately, the palm holds a blue substituent rather than a red one, with the red substituent exposed.

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