StereoChemistry : Chiral Molecules

-identify, categorize, name chiral molecules

-how chirality can affect chemical and
biochemical behavior of organic compounds
_
Chirality- object that can not be superposed
on each other on its mirror image
Ex: hands , mirror image left and right hands,
bu not superposable
What causes some molecules to be chiral?
Isomer- different compounds with same
molecular formula
Constitutional Isomers- have the same
molecular formula but different connectivity
Ex. Butane and 2-methylpropan are both
C4H10
Stereoisomers- have their atoms connected in
same sequence, but duffer in arrangement of
their atoms in space

STEREOCHEMISTRY- consideration of spatial

aspects of molecular structure
~~
Stereoisomers Enantiomers and
Diastereomers
Enantiomers- stereoisomers whose molecules
are nonsuperposable images of each other
Diastereomers-stereomisomers whose
molecules are not mirror images of each other
- Cis and trans alkene isomers are
diastereomers
- Cis and trans cycloalkane isomers are
diastereomers

Enantiomers occur only with compounds

that are chiral
Achiral molecules cannot be enantiomers
A chiral molecule and its mirror image are : a
parit of enantiomers
Relationship is enantiomeric
MOLECULES HAVING ONE CHIRALITY CENTER
OARE CHIRAL
-a chirality center= a tetrahedral carbon atom
that is bonded to four different groups
-molecules with only one chirality center
can exist as pair of enantiomers
*designated with an aterisk*
-important property of enantiomer with a
single chiral center: interchanging any two
groups at chirality center converts one
enantiomer in the other

-any atom at which an interchange of groups

produces a stereoisomer is a stereogenic
center
-interchanging groups is can be done
requires breaking covalent bonds needs
energy dont convert spontaneously
- if two or more groups attached are the
same, no chiral center achiral molecule
Tetrahedral vs. Trigonal Stereogenic Centers
- Chirality centers are tetrahedral
stereogenic centers
- Trigonal stereogenic centers are not
chiral cis and trans alkene isomers
contain these
HOW TO TEST FOR CHIRALITY: PLANES OF
SYMMETRY
-ultimate way to test for chirality is to
construct models of molecule and its mirror
image- then determine whether they are
superposable

-Other aids that can help us recognize

presence of single chiral center
-PLANE OF SYMMETRY imaginary plane that
bisects molecule two halves of molecule are
mirror images

NAMING ENANTIOMERS: THE R,S-SYSTEM

-naming two enantiomers with only iupac
system will have same name ex

2- butanol :
- R,S- system (right, left (sinister is left in
latin)

How to Assign (r) and (S) configurations:

1.
Each group attached o chiral center
assigned a priority or preference : a,b,c,d
- Based on atomic number of atom
lowest atomic number, lowest priority
2.
If two of the atoms ar the same
(example, the methyl and ethyl of 2butanol), priority based on the first point
of difference with the next atoms
connected to it (ex methyl : hhh, ethyl:
chh- ethyl higher priority)
3.
Rotate the model / formula away so
that group with lowest priority is away
from us

4.
Trace path from a to b to c. if direction
is CLOCKWISE, it is (R) !!!
- If is counterclockwise, IT IS (S)

5.
Groups with double or triple bonds are
given priorities as if both atoms were
duplicated or triplicated:

PROPERTIES OF ENANTIOMERS : OPTICAL

ACTIVITY

Pure enantiomers have IDENTICAL

melting and boiling points
-also have many identical properties
Mixtures of enantiomers of a compounds
will have different properties than pure
samples of each
- Enantiomers show different behavior
when they interact with other chiral
substances

-Enantiomers differ in their behavior

toward plane-polarized light
- when beam of plane polarized light
passes through enantiomer, plane of
polarization ROTATES
- separate enantiomers rotate the
plane but in opposite DIRECTION
- separate enantiomers are OPTICALLY
ACTIVE COMPOUNDS
Plane polarized Light

- Consists of electric and magnetic

oscillating field (planes are
perpendicular)
- -polarizer interacts with electric field
oscillating all in one plane
POLARIMETER- device used to measure
effect of optically active compounds in
plane polarized light

If cell of polarizer is empty (optically

inactive), will read zero, max amount of
light passing through
-if optically inactive, will have to rotate
polarimeter in order to achieve max
amount of light
-if analyzer rotated in clockwiser
direction, rotation alpha is POSITIVE
DEXTROROTATORY

-if analyzer rotated counterclockwise

directiom, rotation alpha is NEGATIVE
LEVOROTATORY
Specific Rotation
- The number of degrees that the plane of
polarization is rotated as light passes
through solution of enantiomer depends
on number of chiral molecules that it
encounters

Specific rotation = observed rotation /

concentration of solution (g/mL) * the
length of the cell in decimeters
- Also depends on the temperature and
wavelength of light
- There is no correlation between R and S
configurations of enantiomers in which
they rotate
ORIGIN OF OPTICAL ACTIVITY
-measured by degree of rotation through
chiral medium
-a beam of plane polarized light can be
described in terms of circularly polarized light

-optical activity of chiral molecules results

from two counterrotating circularly polarized
beams travel with different velocities through
chiral medium

-achiral molecules do not cause a difference

in velocity so no rotation of plane

RACEMIC FORMS
- An equimolar mixture of two
enantiomers. This mixture causes no net
rotation of pane-polarized light
ENANTIOMERIC EXCESS
- A sample of optically active substance
that consists of a single enantiomer
enantiomerically pure or have an
enantiomeric excess of 100%. Also
known as OPTICAL PURITY
-

If enantiomeric excess of mixture is 50%, 50%

of mixture is enantiomer excess, 50% is in
racemic form

SYNTHESIS OF CHIRAL MOLECULES

-Racemic Form
When achiral reactants used in reaction, in
absence of any chiral influence from catalyst,
reagent, solvent, outcome of such a reaction
is a racemic mixture
STEREOSELECTIVE SYNTHESES
Stereoselective reactions reactions that ead
to a preferential formation of one
stereoisomer over another that could possibly
be formed
- If a reaction produces preferentially one
enantiomer over its mirror image,
reaction is ENANTIOSELECTIVE
REACTIOn
- If reaction produces one diastereomer
over others that are possible, reaction is
DIASTEREOSELECTIVE REACTION
- For reaction to be either, a chiral
reagent, catalyst, or solvent must assert
influence on course of reaction
chiral influences in nature are ENZYMES.

Enzymes have ability to assert dramatic chiral

influence on reaction enzymes are chiral and
have active site where reactant molecules are
momentarily bound while reaction takes
place.
Active site is chiral only one enantiomer of
chiral reactant fits it property and can
undergo reaction
Ex. Lipase catalyzes hydrolysis ester
reacts with molecule of water to produce
carboxylic acid and alcohol
-if starting ester is chiral, present as mix of
enantiomers, lipase enzyme reacts selectively
with one enantiomer to release the
corresponding chiral carboxylic acid and
alcohol.

Kinetic resolution where the rate of a

reaction with one enantiomer is different than
the other, leading to a preponderance of one
product
CHIRAL DRUGS

- Drugs that contain a single enantiomer

rather than a racemate.
- Penicillamine s isomer has highly potent
therapeutic agent for primary chronic
arthritis, r isomer has no action, very
toxic
- Ibuprofen only s enantiomer is active.
MOLECULES WITH MORE THAN ONE
CHIRALITY CENTER
- In compounds whose stereoisomerism is
due to chirality ceners, the total number
of stereoisomer will not exceed 2^n
where n is equal to the number of
chirality centers
- Stereoisomers for two chirality centers =
2^2 =4
HOW TO DRAW STEREOSIOMERS FOR
MOLECULTS WITH MORE THAN ONE CHIRALITY
CENTER
1.
Draw portion of carbon skeleton that
contains the chirality centers in such a
wat that as many of the chirality centers

are placed in the plane of paper as

possible and as symmetrically as possible
2.
Add remaning groups that are bonded
at te chirality centers in such a way asto
maximize the symmetry between chirality
centers.
3.
To draw enantiomer of first
stereoisomer, draw mirror image side by
side or top and bottom
4.
To draw another stereoisomer,
interchange two groups at any one of the
chirality center
a.
All possible stereoisomers for
compoin can be srawn by successively
interchanging two groups at each
chirality center
5.
Examine relationship between all
pairings to determine which are
enantiomers, which are diasteromers, and
which are identical