Fischer Projections

Flat drawing that represents a 3D molecule

A chiral carbon is at the intersection of horizontal
and vertical lines.
Horizontal lines are forward, out-of-plane.
Vertical lines are behind the plane.
Fischer Rules
Carbon chain is on the vertical line.
Highest oxidized carbon at top.
Rotation of 180 in plane doesnt change molecule.
Do not rotate 90!
(R)-(+)-glyceraldehyde

(S)-(-)-glyceraldehyde
 Fischer Mirror Images
Easy to draw, easy to find enantiomers, easy to find internal
mirror planes.
CH3 CH3 CH3
Examples:
H Cl Cl H H Cl
Cl H H Cl H Cl
CH3 CH3 CH3

Fischer (R) and (S) (S)

CH3
Lowest priority (usually H) comes
forward, so assignment rules are H Cl
backwards! Cl H
Clockwise 1-2-3 is (S) and
CH3
counterclockwise 1-2-3 is (R). (S)
Assigning R and S Configuration to Fischer Projections

1. Assign priorities to the four substituents according to the Cahn-Ingold-

Prelog rules
2. Perform the two allowed manipulations of the Fischer projection to place
the lowest priority group at the top or bottom.
3. If the priority of the other groups 123 is clockwise then assign the
carbon as R, if priority of the other groups 123 is counterclockwise
then assign the center as S.
2
place at
CO2H the top 4
H
1 H2N H 4 2 HO2C NH2 1
hold steady CH3
CH3
rotate other 3 3
three groups
counterclockwise
1-2-3 counterclockwise = S
2
4 2
CO2H
H CO2H
4 H 1 2
NH2 1 H2N
H2N CO2H CH3
CH3 1 3
CH3 H
3 4
3

1-2-3 clockwise = R
Fischer projections with more than one chiral center:

(2S)

(3R)
Draw Fischer Projections given chiral compounds

CH3
HO
H2N CH3 Cl H

H OH NH2

H3C Cl
CH3

H OH H Cl
Cl H

HO Cl
H3C CH3
HO H
HO Cl
 Assigning R and S Configuration to Fischer Projections

CH3

R
F OH S
S
S
Cl H S
R
CH3
R
S

R
 Ques%on Draw the Fischer of the following molecules

A HO
H A HO H

F H
F
H

F OH
B H D
D H
B
H Cl

Cl H HO F

HO F

F HO Cl OH
C Cl H
C
HO Cl

I F
H Cl F I
 Conformers of Alkanes
Structures resulting from the free rotation of a C-C
single bond or Different arrangement of atoms
resulting from bond rotation
May differ in energy. Molecules constantly rotate
through all the possible conformations.
Conformations can be represented in 2 ways:
 Conformers of Alkanes
We do not observe perfectly free rotation
There is a barrier to rotation, and some conformers are
more stable than others
Staggered- most stable: all 6 C-H bonds are as far away as
possible
Eclipsed- least stable: all 6 C-H bonds are as close as
possible to each other
H H H H
H
H H H
H H H H H H
H H H H HH HH
H H
sawhorse Newman sawhorse Newman
staggered eclipsed
 Conformations of ethane

ethane
Staggered Eclipsed
conformation conformation
of ethane of ethane

Newman Sawhorse Newman Sawhorse

Projection Representation Projection Representation
Conforma%ons of Butane

butane
Staggered Eclipsed
conformation conformation
of butane of butane
 Newman and Sawhorse projection
CH3
HH HH H H
Newman projection

H
H3C CH3 H
CH3
H H H H

CH3 Sawhorse projection

H H CH CH3
3

H H
CH3

Eclipsed Staggered
 Interconversions

Fischer Sawhorse

COOH H OH
H OH

H OH
H
OH COOH

COOH COOH
 Interconversions

Sawhorse Fischer

H CH3
Br
H Br
Br Br
H CH3 H

CH3 CH3
 CH2OH H
H
Cl

H Cl
H Br
CHO
CHO CH2OH
Fischer Newman
H Cl

H CH2OH
Br

CHO Sawhorse
 Ethane Conformers
Staggered conformer: Lowest energy; Dihedral angle = 60
Eclipsed conformer has highest energy; Dihedral angle = 0
 Conformational Analysis
Torsional strain: resistance to rotation.
For ethane, only 3.0 kcal/mol
 Propane Conformers
Note slight increase in torsional strain due to the more
bulky methyl group.
 Butane Conformers
Highest energy has methyl groups eclipsed.
Steric hindrance
Dihedral angle = 0 degrees

totally eclipsed
 Butane Conformers
Lowest energy has methyl groups anti.
Dihedral angle = 180 degrees

anti
 Butane Conformers
Methyl groups eclipsed with hydrogens
Higher energy than staggered conformer
Dihedral angle = 120 degrees

eclipsed
 Butane Conformers
Gauche, staggered conformer
Methyls closer than in anti conformer
Dihedral angle = 60 degrees

gauche
Conformational Analysis
Cycloalkanes and their Stereochemistry
Saturated cyclic hydrocarbons are defined as a carbon
ring which has hydrogen in every position except the
attachment point. These are also called alicyclic
compounds.

H H
H H Cyclopropane
H
H H
Cyclo = the cyclic ring
H H
H
H H propane = the number of
carbons
 Basic Examples of Cycloalkanes
Number of Carbons

3 4 5 6 7 8 9 10

Prop But Pent Hex Hept Oct Non Dec

Example: Cyclohexane = a ring of six carbons

 Naming Cycloalkanes
Rule 1 Find the parent: Count the number carbons in the chain
and the substituents. If the substituents is longer than the ring then
the parent name is the substituent. If the ring is longer then the
ring is the parent.

CH2CH2CH2CH3
CH3

1-Methylcyclopentane 1-Cyclopropylbutane

If we look at the molecule on the left. A pentane ring has 5 carbons

compared to its substituent (1 carbon) a methyl. So the parent is the
cyclopentane. However on the molecules on the right butane (4 carbons)
is larger than cyclopropane (3 carbons) so the butane is the parent name.
 Rule 2: Number the substituents, and write the name.
Make sure that you follow the ring so that the substituents have
the lowest numbers.
Number the Substituents. C-1 always has a substituent attached. Number
so that the second substituent has the lowest number possible, etc,

CH3
4
5 3

1 2

H3C CH3

1,2,4-
trimethylcyclopentane

Not 1,3,4-
trimethylcyclopentane
 Rule 3: If two or more alkyl groups have potentially the same
number, number alphabetically.

CH3 1-ethyl-2-
CH2CH3 methylcyclohexane

Not 1-methyl-2-
ethylcyclohexane

Rule 4: Treat other substituents exactly like alkyl groups.

CH3
Br

1-Bromo-2-methylcyclohexane
Example for practice:
 Cis-Trans Isomerism in Cycloalkanes

Cycloalkanes are less flexible than open-chain alkanes

Much less conformational freedom in cycloalkanes
Because of their cyclic structure, cycloalkanes have 2 faces
as viewed edge-on top face bottom face
Because ring dont rotate freely in space like linear chains
two different possibilities exist.
Cis Isomers are when two atoms are on the same side of a ring.
Trans Isomers are when two atoms are on different side of a
ring.

H
H
H
H
H H H
H

Cis Isomers Trans Isomers

 Ring Strain in Cycloalkanes
Types of Strain
Angle Strain or Ring Strain is the strain induced in a molecule
when the bond angles are different from the ideal tetrahedral
bond angle of 109.5. (expansion or compression of bond
angles.)

Torsional Strain is caused by repulsion between the bonding

electrons of one substituent and the bonding electrons of a
nearby substituent.

Steric Strain is caused by atoms or groups of atoms

approaching each other too closely.
Angle (Ring) Strain

Cyclopropane has angles of 60o when we know that SP3 carbons

like to bond at 109.5o. In cyclopropane there is angle strain.

expansion or compression of bond angles away from most stable

Example cyclopropane and cyclohexane:

60o
~109.5o
 Torsional Strain
Is the strain due to eclipsing of bonds on neighboring
atoms.
When atoms are eclipsed then there is a natural tendency
to move away from each other this is called torsional
strain.

H H
H H H H
H
H H H H
H H H
H
H H H
Steric Strain
Steric strain focuses on the strain of functional groups bound due to
size onto the cyclic ring. Because rings dont rotate freely in space
like linear chains then energy is higher when they are on the same
side.
repulsive interactions between nonbonded atoms in close proximity
For example: cyclopropane

H
H
H
H
H
H H
H
Higher Energy Lower Energy
 Stability of Cycloalkanes: Ring Strain
Rings larger than 3 atoms are not flat
Cyclic molecules can assume nonplanar conformations to
minimize angle strain and torsional strain by ring-puckering
Larger rings have many more possible conformations than
smaller rings and are more difficult to analyze