Stereokimia

Tujuan
Mahasiswa dapat menentukan pusat kiral dan
akiral dari struktur molekul organik
Mahasiswa dapat menentukan arah putar (R
atau S) suatu molekul kiral dengan aturan
Cahn Ingold Prelog
Mahasiswa dapat menjelaskan perbedaan
enantiomer dan diastereomer
Isomer
 Constitutional Isomers
Isomers are different compounds with the same
molecular formula.

The two major classes of isomers are constitutional

isomers and stereoisomers.

Constitutional/structural isomers have:

different IUPAC names
same or different functional groups
different physical properties
different chemical properties

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 Stereoisomers
Stereoisomers:

Differ only in the way the atoms are oriented in space.

Have identical IUPAC names (except for a prefix like

cis or trans).

Always have the same functional group(s).

Differ in configuration (its particular three-

dimensional arrangement).

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 Constitutional and Stereoisomers

Figure 5.3

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Contoh
 Nonsuperimposable Mirror Images
Although everything has a mirror image, mirror images may or
may not be superimposable.
Some molecules are like hands. Left and right hands are mirror
images, but they are not identical, or superimposable.
A molecule (or object) that is not superimposable on its mirror
image is said to be chiral.

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 Superimposable (Achiral) Objects
Other molecules are like socks.
Two socks from a pair are mirror images that are
superimposable.
A sock and its mirror image are identical.

A molecule or object that is superimposable on its mirror

image is said to be achiral.

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 Achiral Molecules
We can now consider several molecules to determine
whether or not they are chiral.

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 Chiral Molecules
The molecule labeled A and its mirror image labeled B are not
superimposable.
No matter how you rotate A and B, all the atoms never align.
Thus, CHBrClF is a chiral molecule, and A and B are different
compounds.
A and B are stereoisomersspecifically, they are enantiomers.
A carbon atom with four different groups is a tetrahedral stereogenic
center.

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 Stereogenic Centers

In general, a molecule with no stereogenic centers will

not be chiral (exceptions to this will be considered in
Chapter 17).

With one stereogenic center, a molecule will always be

chiral.

With two or more stereogenic centers, a molecule may or

may not be chiral.

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 Tentukan senyawa berikut kiral atau akiral
 Planes of Symmetry
A plane of symmetry is a mirror plane that cuts the molecule in
half, so that one half of the molecule is a reflection of the other
half.
Achiral molecules usually contain a plane of symmetry but chiral
molecules do not.

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 Stereogenic Centers
To locate a stereogenic center, examine each tetrahedral
carbon atom in a molecule, and look at the four groups
not the four atomsbonded to it.

Always omit from consideration all C atoms that cannot

be tetrahedral stereogenic centers. These include:
CH2 and CH3 groups
Any sp or sp2 hybridized C

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 Multiple Stereogenic Centers

Larger organic molecules can have two, three, or even

hundreds of stereogenic centers.

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 Drawing Enantiomers
To draw both enantiomers of a chiral compound such as
2-butanol, use the typical convention for depicting a
tetrahedron.
To form the first enantiomer, arbitrarily place the four
groupsH, OH, CH3 and CH2CH3on any bond to the
stereogenic center.
Then draw the mirror image.

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 3-D Representation of Enantiomers

Figure 5.5

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 Contoh
Locate the stereogenic center in each
compound and draw both enantiomers.
a. CH3CH(Cl)CH2CH3
b. CH3CH2CH(OH)CH2OH
c. CH3SCH2CH2CH(NH2)COOH
 Stereogenic Centers on Rings
Stereogenic centers may also occur at carbon atoms that
are part of a ring.
To find stereogenic centers on ring carbons, always draw
the rings as flat polygons, and look for tetrahedral
carbons that are bonded to four different groups.

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 Stereogenic Centers

In 3-methylcyclohexene, the CH3 and H substituents that

are above and below the plane of the ring are drawn with
wedges and dashes as usual.

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 Contoh
Tentukan molekul berikut kiral atau akiral. Jika
kiral, tentukan pusat stereogenic nya (tandai
dengan *).
Tata Nama untuk Pusat Stereogenic
Karena enantiomer merupakan dua senyawa
yang berbeda, maka perlu diberikan pembeda
pada namanya
Hal ini dilakukan dengan menambahkan prefix
R atau S pada nama IUPAC nya.
Pemberian R dan S dilakukan berdasarkan
kaidah Cahn Ingold Prelog
Tata Nama untuk Pusat Stereogenic
1. Perhatikan setiap atom yang terikat pada pusat atom
kiral
2. Berikan skala prioritas (1, 2, 3, dan 4) sesuai urutan no
atom. No atom paling kecil mendapatkan prioritas 4
3. Jika ada 2 atom yang sama terikat pada pusat kiral,
prioritas ditentukan berdasarkan atom yang terikat
berikutnya pada atom tsb
4. Atom dengan prioritas paling kecil harus berada di
belakang
5. Lihat arah putar dari prioritas 123, jika searah
jarum jam R, berlawanan arah S
 Assigning Priority for R and S
If two atoms on a stereogenic center are the same, assign
priority based on the atomic number of the atoms bonded
to these atoms.
One atom of higher atomic number determines the higher
priority.

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 Assigning Priority for R and SIsotopes
If two isotopes are bonded to the stereogenic center,
assign priorities in order of decreasing mass number.
Thus, in comparing the three isotopes of hydrogen, the
order of priorities is:

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Assigning Priority for R and SMultiple Bonds
To assign a priority to an atom that is part of a multiple bond,
treat a multiply bonded atom as an equivalent number of
singly bonded atoms.
For example, the C of a C=O is considered to be bonded to
two O atoms.

Other common multiple bonds are drawn below:

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 Assigning Priorities to Stereogenic Centers

Figure 5.6

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How To Assign R or S

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How To Assign R or S

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How To Assign R or S

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Orienting the Lowest Priority Group in Back
If the lowest priority group is not facing towards back, rotate
the molecule 120o around a stationary bond axis.
Figure 5.7

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Contoh
 Finding All Possible Stereocenters
For a molecule with n stereogenic centers, the maximum
number of stereoisomers is 2n.
Let us consider the stepwise procedure for finding all the
possible stereoisomers of 2,3-dibromopentane.

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 Finding All Possible Stereocenters
After drawing the compound and the mirror image, place B
directly on top of A; and rotate B 180 and place it on top of A
to see if the atoms align.

In this case, the atoms of A and B do not align, making A and

B nonsuperimposable mirror imagesi.e., enantiomers.
A and B are two of the four possible stereoisomers of 2,3-
dibromopentane.
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 Finding All Possible Stereocenters
Switching the positions of H and Br (or any two groups) on one
stereogenic center of either A or B forms a new stereoisomer
(labeled C in this example), which is different from A and B.
The mirror image of C is labeled D.
C and D are enantiomers.
Stereoisomers that are not mirror images of one another are called
diastereomers.
A and C are diastereomers.

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 Summary of Stereoisomers of
2,3-dibromopentane
Figure 5.8

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 Contoh

Find all the stereoisomers of 2,3-dibromobutane.

Since this molecule has two stereogenic centers,
the maximum number of stereoisomers is 4.
 Meso Compounds
Senyawa C memiliki potongan simetris (plane of simmetry) dan
akiral
Senyawa meso adalah senyawa akiral yang memiliki pusat
stereogenik, seperti pada senyawa C.
Senyawa meso biasanya memiliki belahan identik (simetris).

Because one stereoisomer of 2,3-dibromobutane is

superimposable on its mirror image, there are only three
stereoisomers, not four. 40
 Stereoisomers of 2,3-dibromobutane

Figure 5.9

Pair of enantiomers: A and B.

Pairs of diastereomers: A and C; B and C.
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 R and S Assignments in Compounds with Two or
More Stereogenic Centers
Pada senyawa yang memiliki lebih dari 1 pusat stereogenik,
konfigurasi R dan S perlu disebutkan dengan jelas (diberi nomor)

One stereoisomer of 2,3-dibromopentane

(2S,3R)-2,3-dibromopentane

Jika R, S memiliki nomor yang sama senyawa yang sama

Jika R, S nya berkebalikan Enantiomers
Jika salah satu R,S nya sama, dan salah satu R,S nya berbeda
Diastereomers

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 Stereokimia Sikloalkana Tersubstitusi
Bagaimana stereokimia untuk sikloalkana yang
tersubstitusi 2 gugus fungsi (disubstitute)?
Contoh:

Posisi atom Br dapat berupa cis atau trans

Cis-1,3-dibromosiklopentana
 Trans-1,3-dibromosiklopentana

Jadi struktur 1,3-dibromosiklopentana hanya

memiliki 3 stereoisomer.
Isomer
 Optical Activity
Dua buah senyawa enantiomer memiliki sifat fisik
yang sama, kecuali interaksinya dengan bidang
polarisasi (plane-polarized light)
Perbedaan ini dapat dilihat melalui polarimeter
A polarimeter is an instrument that allows
polarized light to travel through a sample tube
containing an organic compound and permits the
measurement of the degree to which an organic
compound rotates plane-polarized light.
 Plane-Polarized Light
With achiral compounds, the light that exits the sample tube
remains unchanged.
A compound that does not change the plane of polarized light
is said to be optically inactive.

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 Rotation of Plane-Polarized Light
With chiral compounds, the plane of the polarized light is
rotated through an angle .
The angle is measured in degrees (), and is called the
observed rotation.
A compound that rotates polarized light is said to be optically
active.

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 Optical Activity Summary
The rotation of polarized light can be clockwise or
anticlockwise.
If the rotation is clockwise, the compound is called
dextrorotatory. The rotation is labeled d or (+).
If the rotation is counterclockwise, the compound is called
levorotatory. The rotation is labeled l or (-).
Two enantiomers rotate plane-polarized light to an equal
extent but in opposite directions. (e.g., if enantiomer A
rotates polarized light +5, the same concentration of
enantiomer B rotates it 5).
No relationship exists between R and S prefixes and the (+)
and (-) designations that indicate optical rotation.

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 Racemic Mixtures

An equal amount of two enantiomers is called a racemic

mixture or a racemate.

A racemic mixture is optically inactive.

Because two enantiomers rotate plane-polarized light to

an equal extent but in opposite directions, the rotations
cancel, and no rotation is observed.

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Racemic Mixtures

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 Racemic Mixtures
Specific rotation is a standardized physical constant for the
amount that a chiral compound rotates plane-polarized
light.
Specific rotation is denoted by the symbol [] and defined
using a specific sample tube length (l, in dm),
concentration (c in g/mL), temperature (25C) and
wavelength (589 nm).

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 Optical Purity

Enantiomeric excess (optical purity) is a measurement of

how much one enantiomer is present in excess of the
racemic mixture.
It is denoted by the symbol ee.

ee = % of one enantiomer - % of the other enantiomer.

Consider the following exampleIf a mixture contains

75% of one enantiomer and 25% of the other, the
enantiomeric excess is 75% - 25% = 50%.
Thus, there is a 50% excess of one enantiomer over the
racemic mixture.

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 Enantiomeric Excess

The enantiomeric excess can also be calculated if the

specific rotation [] of a mixture and the specific rotation
[] of a pure enantiomer are known.

ee = ([] mixture/[] pure enantiomer) x 100%.

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 Physical Properties of Stereoisomers
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 techniques.

Figure 5.12

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 Chemical Properties of Enantiomers
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.

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PR