Enantiomers, Diastereomers & Meso Compounds

Enantiomers, Diastereomers & Meso Compounds

Session Objectives

By the end of this
session, students will be able to:

• Explain configuration of enantiomers

• Classify Enantiomers and Diastereomers

• Assign D and L system to isomers

• Define meso compounds

Optical activity

• A solution of optically active molecule (enantiomer) is
placed in a sample tube, plane-polarized light is passed through the tube and a
rotation of the polarization plane takes place

• The light then goes through a second polarizer called an
analyser

• By rotating the analyser until the light passes through
it, the new plane of polarization can be found, and the extent of rotation that
has taken place can be measured

Optical activity

• A mixture of enantiomers with the same amount of each is
called a racemic mixture

• Racemic mixtures are optically inactive (i.e. they cancel
each other out) and are denoted by (±)

Note: the amount
of rotation depends on sample concentration and sample path length

• To obtain a meaningful optical rotation data, we have to
choose standard conditions

• The specific rotation of a compound, designated as [α]D, is defined as the
observed rotation, when the sample path length l is 1 dm, the sample
concentration C is 1g/mL and light of 599.6 nm wavelength (the D line of a
sodium lamp, which is the yellow light emitted from common sodium lamps) is
mostly used

Specific Rotation

• As the specific rotation also depends on temperature, the
temperature at which the rotation is measured and denoted more precisely as

Enantiomers can be described as (+) or (-)

• We can use the fact that two enantiomers rotate
plane-polarized light in opposite directions to assign each a label that
doesn’t depend on knowing its configuration

• We call the enantiomer that rotates plane-polarized light
to the right (gives a positive rotation) the (+)-enantiomer (or the dextrorotatory enantiomer)

• And the enantiomer that rotates plane-polarized light to
the left (gives a negative rotation) the (–)-enantiomer (or the laevorotatory enantiomer)

Enantiomers and Diastereomers

• In general molecule with n chiral centers, the maximum
number of stereoisomers possible is 2n

• That means for one chiral center its 2, for 2 its 4, for 3
its 8 and so forth

• Let us consider 2,3,4-trihydroxybutanal

Enantiomers and Diastereomers

• In general molecule with n chiral centers, the maximum
number of stereoisomers possible is 2n

• Let us consider 2,3,4-trihydroxybutanal

• It contains two chiral centers and 4 stereoisomers are
possible

Enantiomers and Diastereomers

• Stereoisomers (a) and (b) are nonsuperposable mirror
images and are, therefore, a pair of enantiomers

• Stereoisomers (c) and (d) are also nonsuperposable mirror
images and are a second pair of enantiomers

• On naming, enantiomers (a) and (b) as (2R,3R)-erythrose
and (2S,3S)-erythrose; enantiomers (c) and (D) as (2R,3S)-threose and (2S,3R)-threose

• Both belongs to the class of carbohydrates and erythrose
is present in erythrocytes (red blood cells)

• What is the relationship between (a) and (c), (a) and (d),
(b) and (c), (b) and (d)?? Answer is diastereomers

• Diastereomers are the stereoisomers that are not mirror
images

• Molecules with at least two chiral centers can have
diastereomers

Meso compounds

• Molecules containing two or more chiral centers have
special symmetry properties that reduce the number of stereoisomers to fewer
than the maximum number predicted by the 2n rule

• For example, 2,3-dihydroxybutanedioic acid commonly called
as tartaric acid

Meso compounds

• In tartaric acid, carbons 2 and 3 are chiral centers,
number of stereoisomers possible is 4

• (a) and (b) are nonsuperposable mirror images, enantiomers

• (c) and (d) are superposable mirror images, meso compounds

• Also (c) has plane of symmetry and is achiral

• A meso compound contains two or more chiral centers and is
achiral

• To be a meso compound, molecule must also have chiral
isomers

• Hence, tartaric acid has three stereosisomers, one pair of
enantiomers and a meso compound

• Enantiomers of tartaric acid will have same melting point,
boiling point, solubility in water and other common solvents, same value of pKa,
and they undergo the same acid-base reactions

• But differ in optical activity

• Diastereomers have different physical and chemical
properties, even in achiral environments

• Meso tartaric acid has different physical properties from
those of the enantiomers and can be separated from them by methods such as
crystallization

Physical properties of tartaric acid

Physical properties of tartaric acid

Summary

• Enantiomer that rotates plane-polarized light to the right
(gives a positive rotation) the (+)-enantiomer (or the dextro-rotatory enantiomer)

• Enantiomer that rotates plane-polarized light to the left
(gives a negative rotation) the (–)-enantiomer (or the laevo-rotatory
enantiomer)

• The direction in which light is rotated is not dependent
on whether a stereogenic centre is R or S

• Optical activity does not tell us the actual configuration
of an enantiomer

• In general molecule with n chiral centers, the maximum
number of stereoisomers possible is 2n

• Diastereomers are the stereoisomers that are not mirror
images

• Molecules with at least two chiral centers can have
diastereomers

• A meso compound contains two or more chiral centers and is
achiral