Stereochemical formula:

“It is a three dimensional representation of molecular species either as projection on

plane using conventional or bold lines to show orientation of the bond towards the front
and back of the plane.”
There are two ways to represent a stereochemicalFormula:

 Perspective formula
 Fischer projection Formula

Perspective formula:

“A structural formula representing three dimensions and primarily used to distinguish among
optical isomers to compare projection Formula.”

In perspective formula solid lines show plane, wedge lines show groups towards observer and
hatched lines show behind the plane or away from observer.

Example:

Fischer projection Formula:

“A Fischer projection Formula is a convention used todepict a stereochemical Formula in two

dimensional spaces without destroying stereochemicalinformationat chiral center.”

Introduction:
Fischer projection devised by Emil Fischer in 1891. It is a two dimensional representation of a
three dimensional organic molecule by projections. Originally proposed for depiction of
carbohydrates in organic chemistry and bio chemistry.
Need for projection Formula:
 Projection Formula used to represent 3D molecule in two dimension so, it is easier to
draw on paper.
 Newman’s projection and sawhorse projection are not able to explain molecule in two
dimensional spaces . To overcome this difficulty we use ,so called Fischer projection
Formula.

Example:

Rules for Fischer projection :

To convert perspective formula into Fischer projection Formula, following rules are followed:

1. Fischer projection is drawn according to how observer is looking at molecule.

 2. The bonds which are towards the observer always taken on horizontal line and the
bonds which are away or behind from observer taken on vertical line.
3. Highest oxidized carbon is taken on vertical line.

4. Rotation of 180° in plane doesn’t change the configuration of a molecule.

5. If one group is fixed and rotate the other .

Limitations:
There are two limitations of the Fischer projection relating to operations performed on Fischer
projection but without changing the absolute configuration at chiral centers.

 Rotating the entire structure by 180° in either direction does not change the absolute
configuration.
 Rotating three ligands on the chiral centers in either direction, does not change the
absolute configuration at the center.

Configuration:
The arrangements of atoms or groups around assymetric center is
known as configuration.
Types of configuration:
There are two types of configuration:
1) Relative Configuration
2) Absolute configuration

Relative configuration:
Relative configuration describes the spatial position of atoms or groups or
substituents relative to other atoms orgroups in a molecule .

Dependence:
Relative configuration of atoms depends upon the position of other atoms in a molecule.

Example:
  The relative configuration may b cis or trans in a same molecule.
In these examples ,if groups are present in the same side relative to other is known as cis and if
present on the opposite side then they are trans.

 Relative configuration is also present between different chiral centers in the same
molecule.

 Realtive configuration is also present between the pairs of enantiomers .Two

enantiomers of glyceraldehydewere originally arbitrary assigned configurationD and L or
R and S.
 Untill 1950,all configurations were relatiive.Any compound prepared converted into D-
glyceraldehydeto L-glyceraldehyde called relative configuration.

Limitations:Don’t clear the basic defects of D and Lrelative configuration when we study
in structure of more than one stereogeniccentre.

Absolute configuration :
The precise and exact arrangement of atoms or groups or substituents around assymetric
center is known as absolute configuration.
Absolute configuration is independent on groups or position in space .

Rosanoff experiment:
Rosanoff proposed that one compound is chosen as a standard and configuration can be
arbitrary assigned to it .The compound chosen was glyceraldehyde due to its relationship with
sugars labels as (+) and (-) isomers.Once a standard was chosen,other compound could then
related to it.(+) Glyceraldehyde oxidized with mercuric oxide gives (-) Glyceric acid.Both have
same configuration but sign of rotation is different .When the configuration of glyceric acid is
known many other compound then related to it and third configuration is also determined
When a compound is placed in D and L series it’s absolute configuration is also said to be
known.

Bijvoet experiment:
In 1951,it became possible to determine whether Rosanoff guess was right .X-ray

crystallographic technique cannot distinguish between D and L isomer but by using special
technique Bijvoet was able to examine sodium rubidium tartrate and found Rosanoffhad made
correct choice.

R and S Nomenclature:
Introduction:
RS nomenclature is currently the preferred system for assigning absolute configuration
to chiral molecules. The letters R and S come from the Latin words ‘Rectus‘ and
‘Sinister‘ meaning ‘right’ and ‘left’. Molecules that rotate the plane of polarized light to
right are referred to as ‘R isomers’ and the molecules that rotate the plane of
polarized light to left are referred to ‘S isomers’.R-S system is based upon certain rules
devised by R. S. Cahn, Sir Christopher Ingold, and Vladimir Prelog in 1965. They firstly
developed a ranking system to deal with the problem of absolute configurations at a
chiral center. These rules are also known as Cahn-Ingold-Prelog (CIP) rules or
sequencing rules.

Rules of R and S Nomenclature:

Rule no.1 (Atomic numbers):
.Priority is given based on the proton/atomic number (Z) of atoms or groups directly
attached with chiral carbon.
For example:

The chlorine atom (Cl) has an atomic number 17, oxygen (O) has 8, carbon (C) has 6,
and hydrogen (H) has 1. So, Cl is ranked the first position, oxygen, the second, with
methyl the third and hydrogen the last which is entirely not important.This molecule
becomes an ‘R configuration’ compound.

Rule no.2 (Secondary priority):

If two or more of the atoms or groups are the same, the atomic numbers of the
secondary atoms determine the priority order.

For example:

In the above example, both groups (2) and (3) are carbon atoms. But the carbon atom
of group 2 is bonded to another carbon atom and two hydrogen atoms, whereas the
group 3 carbon is directly bonded to three hydrogen atoms only. Thus, ethyl (group 2)
is preferred over methyl (group 3).The molecule has the ‘R configuration’.

Rule no.3 (Point of difference):

If the choice of order is not possible based on the secondary atoms too, priority moves to the
third, fourth, and further atoms until there is a point of distinction.

In the above compound, both groups (2) and (3) have the same first three
attachments, but the third carbon of group 2 is bonded with oxygen and two hydrogen
atom whereas the third carbon of group 3 is bonded to three hydrogen atoms only. So,
group 2 is prior to group 3.Thus, the above compound is an ‘R configurated’ compound.

Rule no.4 (Isotopic priority):

In the case of isotopes, an isotope with a higher atomic mass will have higher priority
over the one with a lower atomic mass.

For example:

The above compound shows an R configuration in nomenclature because deuterium

(1D2) is heavier than hydrogen (1H1).

Rule no.5 (Branches with multiple bonds):

If the branched (secondary) atoms are linked by double or triple bonds, it is counted
twice and thrice. The priority order will drive by the number of bonds.The below is an
'R' configured compound because a triple bond will be prioritized over a double bond.

For example:

Rule no.6 (Rotation of molecules):

After ranking substituents orient the molecules in such a way that the lowest ranked
substituent is pointed away from the viewer if it is not already there as mentioned in
rule zero. The sequence of the other three substituents is noted in the order of
decreasing priority after the lowest priority group is sent back of the plane with dotted
lines (wedged bond).In simple words we rotate the molecule at 180° to make a double
exchange.

For example:

An apparent ‘R configuration’ compound is exposed to be actually an ‘S configuration’

compound.

In the order of decreasing priority if the other three substituents of a rotated molecule
are in a clockwise direction, the absolute configuration is ‘R’. In case if the other three
substituents are in an anticlockwise direction, the absolute configuration will be the ‘S’
one.

For example:
References:Jerry March , Paula Bruiceor https://Psiberg.com.