Biochem - Lesson 2

POWERPOINT PRESENTATION 1
STEREOCHEMISTRY • skeletal isomerism

TOPIC OUTLINE • positional isomerism

1 Stereoisomerism Parent Substituents or
chain branched-chain
2 Isomerism substituents - the
3 Historical Origin of Stereochemistry substances that
are attached to
4 Van’t Hoff and Le Bel
the main
5 Configurations Benzene ring - main compound
compound
* NO2 is in carbon 4
6 How Do We “Draw” a Chirality Centre?
7 How Do We “Name” an Enantiomer?? CONSTITUTIONAL ISOMERISM
8 Cahn - Prelog - Ingold Rules 1 FUNCTIONAL ISOMERISM
→ compounds of identical molecular
STEREOCHEMISTRY formula but which have different
functional groups
→ study of the different structures of the compound e.g., C2H5OH and CH3OCH3
→ chemical reactions that involve in the compound as 2 carbon atoms
the structure differs from its structure 6 hydrogen atoms
1 oxygen atoms
STEREOISOMERISM 2 GEOMETRICAL ISOMERISM
3 OPTICAL ISOMERISM
→ have the same atomic connectivity but differ in the
spatial arrangement of the constituent atoms *1 and 2 are stereoisomerism
→ have the same molecular formula but differ in the
sequence of connectivity or dimensional orientation of ENANTIOMERS
their atoms in space.
→ are stereoisomers that are non-superimposable on
their mirror images
mirror

alanine

*ammonium group are in right and left, respectively

ISOMERISM

ISOMERISM
Iso → the same; similar; equal
Merism → the structural condition of the DIASTEREOMERS
compound
→ are stereoisomers that are not mirror images of
Isomerism → compounds having the same
each other — they are stereoisomers that are not
molecular atoms but different
enantiomers
structure
Isomers → compounds having the same
molecular formula, number of carbon
atoms, hydrogen atoms but different
arrangement, structure
CHIRALITY
THREE MAJOR TYPES OF ISOMERISM
1 CONSTITUTIONAL ISOMERISM → the same as the centrality of the compound
→ a.k.a structural isomers → Molecules that can exist as enantiomers are said to
→ have the same molecular formula but differ be chiral; they are non-superimposable on their mirror
in the sequence in which the individual atoms images.
are bonded (connectivity) → a necessary and sufficient condition for the
existence of enantiomers
→ "cheir" - Greek meaning "hand"

LJR 1
Biochem - Lesson 2
POWERPOINT PRESENTATION 1
→ Molecules that are superimposable on their mirror The two are non-superimposable, mirror images. Such
images are said to be achiral. isomers are called enantiomers.

TETRAHEDRAL STEREOGENIC CENTRES ARE THESE ENANTIOMERS?

→ A carbon atom bonded to four different groups is

called a tetrahedral stereogenic centre, asymmetric
centre, or chirality centre.

(+)-carvone YES!
(+)- Carvone is responsible for the odour of caraway
seed oil. CONFIGURATIONS

STEREOGENIC CENTRES → The particular arrangement of atoms in space that

is characteristic of a given molecule is called its
→ A centre where a swapping of groups leads to a configuration.
stereoisomer: → Configurations are not the same as conformations.
→ Conformations are interconvertible by rotation
about single bond(s) whereas bonds must be broken
to change one configuration into another.
e.g., a compound exposed to radiation, the compound
will spin clockwise (+) or counterclockwise (-)

alanine HOW DO WE “DRAW” A CHIRALITY CENTRE?

*Ammonium group are in right and left, respectively.

HISTORICAL ORIGIN OF STEREOCHEMISTRY

o Only one compound with the formula CH3X is

ever found.
o Only one compound with the formula CH2XY
is ever found.
o Two compounds with the formula CHXYZ are
found — a pair of enantiomers.
→ X is any compound; the formula with unknown → the chirality of the compound is the same; the
compound is X. If there is another compound attached substituent elements change position
which is different from X is Y. If there are still
compound not similar to X and Y is Z.
NOTE
Carbon atom has four electrons in the outermost
shell; it has the capacity to combine with other
elements to justify the outermost shell to become
stable.

VAN’T HOFF AND LE BEL Chiral centre

mirror Fischer structures…

HOW DO WE “NAME” AN ENANTIOMER?

Backbone of
compound A problem...How can we look at two Lewis structures
and decide if they represent two identical compounds
or a pair of enantiomers? How can we name them?

LJR 2
Biochem - Lesson 2
POWERPOINT PRESENTATION 1
Alkane WHY THERE ARE SOME LEFT-HANDED DRUGS AND
C=2 RIGHT-HANDED DRUGS WHICH ARE BOUGHT IN
CnH2n+2 = C2H2(2)+2 = C2H6 * C2H6 (ethane) - one H atom = ethyl STORES?

+H → The packaging in the formulation has L-glucose and

* H and Cl are D-glucose, which means that it is the formulation of
inorganic the compound in that particular drug that you are
+H buying from the drug store. These compounds have
different arrangement, characteristics, chemical
properties because of the conformation of the drug
C=1 itself.
CnH2n+2 = C1H2(1)+2 = CH4 * CH4 (methane) - one H atom = methyl

NOTE
The name of enantiomer is Chloro Ethyl Isopropyl has the same structure with a ketone.
Methylmethane
WHY THERE ARE ISOMERS?
NOTE
Octet Rule: In order for an element to become → because of some factors affecting this compound,
stable, it must contain eight electrons in the when subjected to high temperature or radiation, it
outermost shell. changes structure because the elements composing
these compounds have the tendency to move from
CAHN - PRELOG - INGOLD RULES any place they want or to rotate in their axis. There
would be a formation of different arrangement. Some
CAHN - PRELOG - INGOLD RULES constituent elements of the compound may rotate
Step 1 ASSIGN A PRIORITY TO THE FOUR clockwise or counterclockwise or up and down or cys /
ATOMS OR GROUPS OF ATOMS BONDED trans / iso conformation / enantiomer / diastereomers
TO THE TETRAHEDRAL STEREOGENIC / constitutional isomers would have different
CENTRE: properties. They possess different chemical properties
1. If the 4 atoms are all different, wherein if taken in the body, different reactions in the
priority is determined by metabolism of the body possess.
atomic number. The atom of
higher atomic number has the FACTORS AFFECTING STEREOISOMERISM
higher priority. 1 Radiation
2 High Temperature
→ when hot, the body molecules are moving;
when cold, the body molecules are resting
2. DETERMINATION OF PRIORITY 3 Light
If priority cannot be determined 4 Superimpose
by (1), it is determined by a 5 The compound is cyclo (polygon)
similar comparison of atoms
working out from the TWO MAIN TYPES OF STEREOISOMERISM
stereocentre. 1 Cys - Trans isomers
2 Optical isomerism / enantiomers / chirality

REQUIREMENTS FOR STEREOISOMERISM

1 The carbon of the double bond must have two
different substituent groups (oxygen group,
In the methyl group, the second sulfur, carboxylic acid, amino group, nitrogen,
atoms are H, H, H whereas in chlorine, bromine), one may be hydrogen.
the ethyl group, they are C, H,
H. When speaking of isomerism, chirality is always
The priority sequence is embedded in the discussion. It is an important aspect
therefore Cl, C2H5, CH3, H. in stereoisomerism. Most often the molecules that is
present in an asymmetric carbon atom.
Stereoisomers are isomers that differ in a spatial
arrangement of atoms rather than the order of
connectivity.

LJR 3
Biochem - Lesson 2
POWERPOINT PRESENTATION 1
The rotation of its mirror image does not generate the PRINCIPLES OF COVALENT BONDING
original structure. To superimpose the mirror image 1 The covalency number of the element must be
bonds, must be broken and reformed. In contrast, its justified in order for them to become stable.
mirror image can be rotated so they are 2 The electrons must be justified with a total of
superimposable. eight electrons in the outermost shell.
e.g., bromo chloro fluro methane is a chiral molecule e.g., Carbon has four covalency bonds, there
because they are stereocenters that are designated are four unpaired electrons for carbon. It
with an asterisk. When no generated structure and still needs four electrons coming from another
the original structure, it is called achiral. element to justify the rule of eight (Octet Rule).

NOTE FACTOR AFFECTING THE REARRANGEMENT OR

As a universal rule, no molecule with different CONNECTIVITY OF ATOMS IN SPACE
surrounding atoms are achiral. The chirality is a 1 RADIATION
simple but essential idea to support the concept → once exposed, the compounds will have a
of stereoisomerism, being used to explain one Brownian movement; they will be moving
type of its kind. The chemical properties of the counterclockwise or clockwise and the spin of
chiral molecule differs from its mirror image and these elements attached to the backbone of
in this lies the significance of chirality in relation to the compound, which is the carbon would be
modern organic chemistry. disarrangement. They will be spinning
clockwise with a positive spin or
Organic compounds are made possible by means of counterclockwise having a negative spin.
covalent bonding. 2 TEMPERATURE
Chemical bonds - attractive forces that link atoms → when subjected to high temperature, it
together; mutual sharing of electrons between pairs of would make the compounds different in their
atoms connectivity.
WHY? 3 PRESSURE/MECHANICAL REACTIONS
for the compound to become stable

For organic compounds to become stable they do so

by means of covalent bonds. These are attractive
forces that joins two nonmetals together.

Carbohydrates’, proteins’, lipids’, and nucleic acids’

structure are bonded covalently with a carbon and
with another carbon but other elements. These are
bonded by attractive force, chemical bond. They
become stable and it will be very difficult for these
elements to be broken down to simpler substances.
Not unless it is affected by another element which is
stronger in activity or stronger in reaction.
ANALOGY: Relationship or partners of individuals.
In order for the relationship to become stable, it should
have a mutual sharing, mutual understanding
between partners. If there is a stronger person that will
enter into the relationship, the weaker one will be
replace by the stronger one.

This relationship in humans is govern by the principle

of chemistry which is called chemical bond.

e.g., Water is made up of hydrogen gas and oxygen

gas and because of chemical reactions involved, water
is formed by means of covalent bond. Hydrogen will
share one electron to oxygen since there are two
hydrogens that are required to form the compound,
another hydrogen is needed to justify the valence
electrons coming from the oxygen.

LJR 4