Molecular representation of stereochemical molecules

Since stereochemistry refers to molecules in three dimensions, appropriate

modes of representations of 3D molecules on 2D paper is essential.
Flying wedge notation (mostly used for single asymmetric center)

In the plane of the paper Dash: projecting behind

and in the same plane the plane of the paper Dash and Wedge are on
as the tetrahedral carbon away from you adjacent position off the
(adjacent position off the tetrahedral carbon
tetrahedral carbon) H
Wedge: projecting out
C OH
HO2C of the plane of the paper
CH3
toward you
 H H H
Br
C OH HO C C OH Br
HO2C CO2H HO2C
CH3 H3C CH3

Cl Br Cl
OH OH
Cl O OH
Cl Br H

Correct Incorrect

Interchanging any two groups inverts the stereochemistry.

The “double-switch” does not change the stereochemistry.
 Fischer Projection formula
representation of a three-dimensional molecule as a flat structure.
A tetrahedral carbon is represented by two crossed lines:

horizontal line is coming

out of the plane of the
page (toward you)
vertical line is going back
behind the plane of the substituent carbon
paper (away from you)

CO2H CO2H CO2H

H OH H OH
(R)-lactic acid OH
H3C CH3
H CH3

(S)-lactic acid CO2H CO2H CO2H

H HO H HO H
H3C
OH CH3 CH3
Manipulation of Fischer Projections
1. Fischer projections can be rotated by 180° only!

CO2H CH3 CO2H CH3

180 ° H OH HO H 180 ° HO H H OH
CH3 CO2H CH3 CO2H

(R) (R) (S) (S)

a 90° rotation inverts the stereochemistry and is not permissible

90 ° CO2H OH
H OH ° HO2C CH3
CH3 H

(R) (S)
2. If one group of a Fischer projection is held steady, the other three groups can be rotated
clockwise or counterclockwise.
hold CO2H H
CO2H CO2H
steady HO H HO2C OH
H OH HO CH3 hold CH3 CH3
CH3 H steady
(S) (S)
(R) (R)

Interchanging any two groups inverts the stereochemistry.

The “double-switch” does not change the stereochemistry.
 Newman Projections
Not applicable for a single carbon containing compound.

The front carbon of this bond is represented by a dot, and the back carbon is represented by
a large circle. The three remaining bonds are drawn as sticks coming off the dot (or circle),
separated by one another by 120 degrees. A Newman Projection can be drawn such that the
groups on the front carbon are staggered (60 degrees apart) or eclipsed (directly overlapping)
with the groups on the back carbon.

staggered eclipsed
Newman Projections are used mainly for
determining conformational relationships.
Recall that conformers are molecules that
can be converted into one another by a
rotation around a single bond.

Newman Projections can be made for butane, such that its eclipsed, gauche,
and anti conformations can be seen.
 Sawhorse Projections
• Sawhorse Projections are very similar to Newman Projections, but
are used more often because the carbon-carbon bond that is
compressed in a Newman Projection is fully drawn out in
a Sawhorse Projection.
• Sawhorse Projections are useful for determining enantiomeric or
diasteromeric relationships between two molecules.

staggered eclipsed
• Consider the following molecules and determine whether the Sawhorse
Projection is staggered or eclipsed, how many carbons are in the longest
chain of the molecule, and what other groups are connected to the front
and back carbons?

• This Sawhorse Projection is eclipsed. The longest chain in the molecule

most likely always contains the bond you are looking down.
there are seven carbons in the longest chain, two from the ethyl group on
the back carbon, three from the propanol group on the front carbon, and
two connecting carbons from the Sawhorse Projection. Therefore, the
remaining groups are a hydrogen and a methyl group on the front carbon
and a bromine and an ethyl group on the back carbon.
Cyclic Structures

From left to right, these structures are the Wedge-Dash Notation,

the Haworth Projection, and the Chair Conformation.

First one is cyclic wedge-dash notation. In the structure above, the methyl
group is behind the page. Since there must be four bonds to each carbon,
and two sticks and one dash have already been drawn in, the remaining
hydrogen must be wedged.
 Haworth Projections
• Haworth Projections are similar to the cyclic Wedge-Dash notation,
in that the ring itself is drawn as planar. The groups on a Haworth
Projection are simply oriented perpendicular to the plane of the
ring, either up or down.
 Chair Conformation
• Chair Conformations are the most accurate representations of how
cyclohexane rings are actually oriented in space. They appropriately
reflect the angles between the carbons in the ring and the positions
of the groups on each carbon in the ring.
Conversion of projection formula
• Conversion of Fisher to Wedge.

CO2H CO2H CO2H

H OH H OH
OH
H3C CH3
H CH3

CO2H CO2H CO2H

H HO H HO H
H3C
OH CH3 CH3
Conversion Fischer to sawhorse
Conversion Fischer to Newmann
Configurational Nomenclature
 Appropriate configurational descriptors (name or symbol) is
necessary to distinguish two stereoisomers.
 One must know which structures belong to which enantiomers.

Fischer’s D and L Nomenclature

R and S (CIP Nomenclature)
Threo and Erythro nomenclature
Cis-trans and E Z nomenclature
 Erythreo and Threo nomenclature
• Erythro diastereomers have similar group on same side of the
Fischer Projection.
• Threo diastereomers have similar group on the opposite side of
the Fischer projection.
 R/S Nomenclature
Cahn-Ingold-Prelog system (CIP)
 R-enantiomer (Clockwise Rotation)
S-enantiomer (Counterclockwise Rotation)
Labeling Stereogenic Centers with R or S
• To designate enantiomers as R or S, priorities must be assigned to each group
bonded to the stereogenic center, in order of decreasing atomic number. The
atom of highest atomic number gets the highest priority (1).

I > Br > Cl > S > F > O > N > C > H

Priority Rules for Naming Enantiomers (R or 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
priority determines the higher priority.
 Priority of Isotopes on a Stereogenic Center

• 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:
Priority Rules for Multiple Bonds in (R or S) Labeling
• 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:

Examples Assigning Priorities
R or S Enantiomers
Positioning the Molecule for R/S Assignment
 R-enantiomer (Clockwise Rotation)
S-enantiomer (Counterclockwise Rotation)
Assigning R and S Configuration to Fischer Projections
1. Assign priorities to the four substitutents 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). Very Good rule: Vertical is good
3. If the priority of the groups 123 are clockwise then assign
the center as R, if 123 are 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
 CO2H HC HC CH2
C

C C
H CH3
H3C NH2
H3C-H2C
 E/Z nomenclature
• IUPAC system for naming alkene isomers, called the E-Z system,
is based on the same priority rules. The general strategy of
the E-Z system is to analyze the two groups at each end of the
double bond.
• Higher priority group at one end of the double bond and the
higher priority group at the other end of the double bond are on
the same side (Z, from German zusammen = together) or
on opposite sides (E, from German entgegen = opposite) of the
double bond.
• Ex:
Above Adamentane derivative can be regarded as the
formal derivative of 2-bromopropionic acid
RS Nomenclature of Cyclohexane system