Properties of Chiral Molecules: Optical Activity

A substance is optically active if it rotates the plane of polarized light. In order for a substance to exhibit optical activity, it must be chiral and one enantiomer must be present in excess of the other. Optical Activity

Light has wave properties periodic increase and decrease in amplitude of wave

Light optical activity is usually measured using light having a wavelength of 589 nm this is the wavelength of the yellow light from a sodium lamp and is called the D line of sodium

Polarized light ordinary (nonpolarized) light consists of many beams vibrating in different planes plane-polarized light consists of only those beams that vibrate in the same plane

Polarization of light

Nicol prism Polarization of light

Nicol prism Polarization of light

Rotation of plane-polarized light



observed rotation (  ) depends on the number of molecules encountered and is proportional to: path length (l), and concentration (c) Specific rotation

observed rotation (  ) depends on the number of molecules encountered and is proportional to: path length (l), and concentration (c) therefore, define specific rotation [  ] as: 100  cl concentration = g/100 mL length in decimeters Specific rotation [  ] =

a mixture containing equal quantities of enantiomers is called a racemic mixture a racemic mixture is optically inactive (  = 0) a sample that is optically inactive can be either an achiral substance or a racemic mixture Racemic mixture

an optically pure substance consists exclusively of a single enantiomer enantiomeric excess = % one enantiomer – % other enantiomer % optical purity = enantiomeric excess Optical purity

Since enantiomers have identical physical properties, they cannot be separated by common physical techniques like distillation. Diastereomers and constitutional isomers have different physical properties, and therefore can be separated by common physical techniques. Physical Properties of Stereoisomers Stereochemistry Figure 5.12 The physical properties of the three stereoisomers of tartaric acid

Two enantiomers have exactly the same chemical properties except for their reaction with chiral non-racemic reagents. Many drugs are chiral and often must react with a chiral receptor or chiral enzyme to be effective. One enantiomer of a drug may effectively treat a disease whereas its mirror image may be ineffective or toxic. Chemical Properties of Enantiomers Stereochemistry

Enantiomers and the Sense of Smell Research suggests that the odor of a particular molecule is determined more by its shape than by the presence of a particular functional group. Because enantiomers interact with chiral smell receptors, some enantiomers have different odors. Stereochemistry

Absolute and Relative Configuration

Relative configuration compares the arrangement of atoms in space of one compound with those of another. Absolute configuration is the precise arrangement of atoms in space. Configuration

Relative configuration compares the arrangement of atoms in space of one compound with those of another. until the 1950s, all configurations were relative Absolute configuration is the precise arrangement of atoms in space. we can now determine the absolute configuration of almost any compound Configuration

No bonds are made or broken at the stereogenic center in this experiment. Therefore, when (+)-3-buten-2-ol and (+)-2-butanol have the same sign of rotation, the arrangement of atoms in space is analogous. The two have the same relative configuration. CH 3 CHCH 2 CH 3 OH Pd [  ] ° [  ] ° Relative configuration CH 3 CHCH OH CH 2

HHO HOH H 2, Pd HHO HOH Two possibilities But in the absence of additional information, we can't tell which structure corresponds to (+)-3-buten-2-ol, and which one to (–)-3-buten-2-ol.

HHO HOH H 2, Pd HHO HOH Two possibilities Nor can we tell which structure corresponds to (+)-2-butanol, and which one to (–)-2-butanol.

HHO HOH H 2, Pd HHO HOH Absolute configurations [  ] +33.2° [  ] +13.5° [  ] –13.5° [  ] –33.2°

Not all compounds that have the same relative configuration have the same sign of rotation. No bonds are made or broken at the stereogenic center in the reaction shown, so the relative positions of the atoms are the same. Yet the sign of rotation changes. CH 3 CH 2 CHCH 2 Br CH 3 HBr [  ] -5.8° [  ] + 4.0° Relative configuration CH 3 CH 2 CHCH 2 OH CH 3