CONFORMATION, ISOMERISM

&
STEREOCHEMISTRY

Ainka.brown02@uwimona.edu.jm

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Same atoms.
Connected differently.
Differ by rotation of a single bond.
Can be interconverted.
Same molecule
Same atoms. Same connectivity.
Different 3-D arrangement.
Cannot interconvert by
rotation. Different molecules.
Not mirror images.
Cannot interconvert by
rotation. Different molecules.
Mirror images. 2
Representing 3-D nature of molecules in

Newman
Dash-wedge model projection
sawhorse

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Dash-wedge of ethane

D
D
A
C
Bonds in
E the plane
B
B F

https://www.youtube.com/watch?v=E52oU-pwDxY
Conformations of Ethane- Khan Academy
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Dash-wedge

D
A D
A
C
Bonds in
E the plane
B E
B F

WEDGES
Bonds
coming
towards 5
Dash-wedge
HASHED LINES
Bonds going
behind
D D
A
A
C F
C Bonds in
E the plane
B E
B F

WEDGES
Bonds
coming
towards 6
 Pay attention to direction
ATOMS
1 2
H
* 3
Cl
6
SH
5
4 CH3
NH2
ANSWER
1
2
3
4
5
6 7
 1 2 ATOMS
SH H
H
* Cl
6 Cl CH3 3
SH
CH3 NH2
5
CH3
4
NH2
ANSWER
1 SH
2 H
3 CH3
4 NH2
5 CH3
6 Cl 8
SAWHORSE (rotate to look at carbons along a
bond)
D
D

C E Bonds
looking
A along

B B

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SAWHORSE (rotate to look at carbons along a
bond)
D D

C E C
Bonds
A looking
A along

B
B
FRONT CARBON

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SAWHORSE (rotate to look at carbons along a
bond) BACK CARBON

D
D

E
F F

C E Bonds
A looking
C
A along

B
B
FRONT CARBON

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NEWMAN (abbreviated sawhorse)

D
D

F
E
C E F

CH HA
A A
C

B
B HB

Front carbon 12
NEWMAN (abbreviated sawhorse)

D
D
CIRCLE
F back carbon
E
C E F

CH HA
A A
C

B
B HB
CIRCLE
Front carbon 13
NEWMAN (abbreviated sawhorse)
BONDS FROM
BACK CARBON
D
D
D
F H
E
C E F

CH HA
A A
C
H HE
F
B
B HB

Front carbon 14
 SAWHORSE NEWMAN
D
D

C
F A

C E
E
A F

B B

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 C A
D

F
B
E

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 C A
D
D

F
B E
E F

A
C

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 C A
D
H
F
B
E
CH3

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 C A
D
H
F
B
E
CH3

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Give IUPAC name, sawhorse and Newman
projections

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 Give IUPAC name, sawhorse and Newman
projections

2-bromo-3-fluorobutane

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 Give IUPAC name, sawhorse and Newman
projections

CH3 CH3

* Br H F H

F H Br H
* CH3
CH3
2-bromo-3-fluorobutane

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 Conformational Isomerism
Free rotation about a single bond gives conformers

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 Conformational Isomerism
Free rotation about a single bond gives conformers

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 Conformational Isomerism
Free rotation about a single bond gives conformers

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 Conformational Isomerism
Free rotation about a single bond gives conformers

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27
 *

Staggered conformation (groups 180°) = anti

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 * * *

* * *

Staggered conformation (groups 180°) = anti

Eclipsed conformations

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 * * * *

* * * *

Staggered conformation (groups 180°) = anti

Eclipsed conformations
Staggered conformation (groups 60°) = gauche
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 Conformational Analysis of ethane
Eclipsed Eclipsed

Dihedral angle
(angle between two
groups)

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 Conformational Analysis of ethane
Eclipsed Eclipsed

Dihedral angle
(angle between two
groups)

gauche
anti

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Conformers of butane

Anti Eclipsed Gauche Eclipsed

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Anti Eclipsed Gauche Eclipsed

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Eclipsed This is different from ethane.
The two eclipsed conformers have different energy.
The anti and gauche have different energy.
Why?

Eclipsed

Gauche

Anti

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 ISOMERS
(same number and types of atoms
but different compounds)

CONSTITUTIONAL ISOMERS GEOMETRIC ISOMERS

(atoms have different connectivity) (same connectivity but different 3-D
arrangement due to restricted rotation)

Alkenes
Cis: identical groups Z: priority groups on
on same side same side of double
Trans: identical bond
groups on opposite E: priority groups on trans Z E
cis
sides opposite sides of
double bond 36
 Stereoisomers of Alkenes (geometric isomers)

Molecules having the same constitution but different orientation

or geometry in space

H3C H H3C Br

C C C C
H H
H Br

trans-1-bromopropene cis-1-bromopropene

Br

Br

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 The E-Z System of Nomenclature

Cahn-Ingold-Prelog rules

•Atom with highest atomic number assigned the highest priority #1.

•In case of ties, look at the next atoms along the chain.

•Double and triple bonds are treated like bonds to duplicate atoms.
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• Assigning priority
• 1) Look at atoms directly bonded
to the C=C

• 2) Higher atomic number = higher

priority (#1), other group = #2

• 3) If atoms are the same look for

point of difference (put a dot)
then use rule 2

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 (1)

(2)

IUPAC name for (1) = (Z)-2-bromo-1-chloro-1-fluoroethene

IUPAC name for (2) = (E)-1-bromo-1-chloro-2-methyl-1-butene

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 ISOMERS
(same number and types of atoms
but different compounds)

CONSTITUTIONAL ISOMERS GEOMETRIC ISOMERS

(atoms have different connectivity) (same connectivity but different 3-D
arrangement due to restricted rotation)

Alkenes Cycloalkanes

Cis: identical groups on

same side
Trans: identical groups cis Z cis cis
on opposite sides
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What is chirality?
• Chiral compounds (and objects) are non-superimposable mirror
images

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Chiral molecules
• A molecule and its mirror image represent two different chemical
entities.
• A molecule and its mirror image:
A) have the same molecular formula
B) have the same connectivity of atoms
C) differ in the way in which the atoms are arranged in space.

• The molecule and its mirror image are known as enantiomers.

• One is known as the R-isomer and the other is the S-isomer

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If we rotate B and compare with A, we see
more clearly that:
1) they have different 3-D orientations
2) the molecules are non-superimposable.

A B

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Chirality in everyday life

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How do we know if a molecule is chiral?
• Look for a tetrahedral (sp3 hybridized) atom bonded to four different
groups. This tetrahedral atom is known as the stereocentre

CH3 CH3
NH2 CH2 CH2
H3C C* Cl H3C C CH2 CH3 H3C C * CH2 CH2 CH3
H H H

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Determining whether R or S isomer
• 1) Identify stereocenter Cl

* NH2
H
CH3

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Determining whether R or S isomer
1
• 1) Identify stereocenter Cl

* 2
• 2) Rank groups attached to stereocenter 4H NH2
(use atomic number, point of difference) CH3
3

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Determining whether R or S isomer
1
Cl
• 1) Identify stereocenter
* 2
• 2) Rank groups attached to stereocenter 4H NH2
(use atomic number, point of difference) CH3
3

• 3)Rotate so lowest priority group pointing behind) 1

Cl

* 4
H3C H
3 2
NH2
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 Determining whether R or S isomer
• 1) Identify stereocenter

• 2) Rank groups attached to stereocenter

(use atomic number, point of difference)

• 3)Rotate so lowest priority group pointing behind) 1

Cl

* 4
• 5) 1→ 2 →3 clockwise (right)? H
Or anticlockwise (left)
H3C 2
3
NH2
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 Rectus Sinister
Clockwise/right Anti-clockwise/ left

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 Rectus Sinister
Clockwise/right Anti-clockwise/ left

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 Determining whether R or S isomer
• 1) Identify stereocenter

• 2) Rank groups attached to stereocenter

Clockwise.
(use atomic number, point of difference) Therefore it is the
R-isomer
• 3)Rotate so lowest priority group pointing behind) 1
Cl

* 4
• 5) 1→ 2 →3 clockwise (right)? H
Or anticlockwise (left)
H3C 2
3
NH2
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R or S isomer (#2)
• 1) Identify stereocenter H

* Cl
F
Br

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R or S isomer (#2)
4
• 1) Identify stereocenter H
2
• 2) Rank groups attached to stereocenter 3 * Cl
F
(use atomic number, point of difference) Br
1

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R or S isomer (#2)
4
• 1) Identify stereocenter H

* 2
• 2) Rank groups attached to stereocenter 3F Cl
(use atomic number, point of difference) Br
1

• 3)Rotate so lowest priority group pointing behind) 1

Br
4
3 * H
F 2
Cl 56
 R or S isomer (#2)
• 1) Identify stereocenter

• 2) Rank groups attached to stereocenter

Clockwise.
(use atomic number, point of difference) Therefore it is the
R-isomer
• 3)Rotate so lowest priority group pointing behind) 1
Br
4
• 5) 1→ 2 →3 clockwise (right)? 3 * H
Or anticlockwise (left) F 2
Cl
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 R or S isomer (#3)
4
• 1) Identify stereocenter
1
2 NH2
• 2) Rank groups attached to stereocenter
CH3
(use atomic number, point of difference) 3

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 4
R or S isomer (#3) Ainka this structure is actually R
and needs changing 1
2 NH2
• 1) Identify stereocenter CH3
3
• 2) Rank groups attached to stereocenter
(use atomic number, point of difference)
2
CH2CH3
• 3)Rotate so lowest priority group pointing behind)
4
3 * H
• 5) 1→ 2 →3 clockwise (right)? H3C
1
Or anticlockwise (left) NH2
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 R or S isomer (#3)
• 1) Identify stereocenter

Anticlockwise (left)
• 2) Rank groups attached to stereocenter Therefore it is the S-isomer
(use atomic number, point of difference)
2
CH2CH3
• 3)Rotate so lowest priority group pointing behind)
4
3 * H
• 5) 1→ 2 →3 clockwise (right)? H3C
1
Or anticlockwise (left) NH2
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The (R-S) System
H H

Notice that C CH3 H3C C

CH2CH3
CH3CH2 NH2 H2N
mirror images
will have S mirror plane
R
opposite
configurations.

H H

C Cl Cl C
F F
Br Br
R S
(R)-bromochlorofluoromrthane mirror plane
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Key Words to define
• Chiral
• Achiral (this means not chiral)
• Enantiomers
• Diastereomers
• Racemic mixture
• Stereocentre / Asymmetric carbon

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 D

E
F

A
C

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 OPTION ATOMS
Cl 1 2
A) H
S * * B) Cl
6 3
N
C) SH
5
4 D) CH3
E) NH2

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