STEREOISOMERISM

Isomerism which arises due to difference in

spacial arrangementof atoms and group among
ieomerg having same structure or connectivity or
linkages or bonding pattern
Stereo ieomeriem
D
configurational conformational
D D
Geometrical Diastereomeriem Optical
A a
IgomeriemCOID
Isomerism CG.Ig
All shows few shows

Enantiomerem Epinieseism Anoineriem

Configurational Isomerism

stereoieomeriem which ankes due to difference in

configurations of isomers are called configurational
ieomoriem
Configurations

Different three dimeneional structures of same

molecular and structural formula which
can't be converted into each other without
the chemical reactions i e bond
diee ciation
and formation are called
configuration
Note
Different configurations represents the different
compounds which are ieomer of each other but
not identical
Geometrical Isomerism
stereoisomers em which arises due to difference
in spacial arrangementof different atoms or groups
around two atoms between which there is restricted
rotation is called Geometrical Isomoriem
Condition for G 2
Beeence of two different atoms groups at each
or
end of restricted rotation through the atoms or
groups present at two different end can be game
Note Restricted rotation is caneed due to
C Multiple boned Cii Cyclic structure
Compounds showing G I CauseofRestrictedRotation
1 In alkenes c
2 In cycloalkanes cyclic
3 In cycloalkenes with 8D c c cyclic
4 In alleneswith odd no g nB c

s In spiranescoithodd no ofRinge cyclic

G In diazo compounds H H
7 In oximes ofunsymmetrical
aldehydes ketones
 Geometrical Isomerism in Alkenes
9 9 9
9
49 94 49
a b a
cfbb a
cfb
c
g

GI X x x x
9 9
abecab 96
b
cfb
b a
GI cis Trans
9
ab Cad 94
b
49
d b
cfd
a
GI cis Trans

g e g d

GI
ab Cde
4
bdb_e
4
Can't be danified into
an stairs forme
Relative Configuration of Geometrical Isomers (Cis & Trans form)
It is applicable only when atleaet one atom
or group is identical at two ends
of restricted
rotation
Cie Identical atoneygroupson same side
Trane Identical atomygroups on different
sides
Note It is weed in common naming
G I
Absolute Configuration of Geometrical Isomers (E & Z System)
It is applicable to all kind fo geometrical
ieomers and are cued in their 2 PAC name
for this purpose the two atoms or groups
present at each end of scetoicted rotation are
numbered on the basis
of priority
rules are given by Cahn Ingold Belog
E Entgegen Atoms groups of same
priority on opposite side
2 Gugammers Atoms groups of same
priority on same side
Note E 2 form are independent from cis
and trans forms as E form may be cis
or foam like the 7 form
C.I.P. Rules
1 Only atom directly bonded to G C is compared
and the higher priority is given to atom
with C Higher atomic number
e.g FL AL Br f I
N Hz L H
Hay f OH L OCHS
Higher may number In
calc
of ieotopee
H L D L T
 2
Tf the two atoms are identical same
comparison is done on next and subsequent
atoms on equivalent level
3
Only one single bonded atom of highest
priority is compared at a time
4 Double and triple bonded atoms are
duplicated or triplicated into equivalent
single bonds as follows
O O C
CHO j E d o c
H I
H
c K
H
at g N d HcC
I
e.g CHO f cocky f CON
Hz a Hc
f COOUT
f COOH f CO

S Bond pair is given more priority than lone

pair BP LP
Diastereomerism
Existence of stereoisomers which are neither minor
images of each other nor superimpoeible on
each other
Note All geometrical ieomer are always
diastescomer each other thus called
of
Geometrical Diastereo nor
 Physical Properties of Geometrical Isomers
(A) With Similar groups at two ends of Geometrical Centre

Properties mess cis 2Butene 3,94 493 Trane2Butene gg

c

I Dipolemoment Moretto Lees o

2 Meltingpoint Lees More

CBaledonsymmetnd
3 Boiling point More Lees
Baledonvanderwad
forces
4 Thermal Legg More
stability
5 Heat of More Legg
Hydrogenation
G Solubility in More trees
H2O
(B) With Different groups at two ends of Geometrical Centre
properties mess cis 2Butene 3,94 4,702 Trane2Butene Bc 492
I Dipolemoment L More

2 Meltingpoint Lees More

CBaledonsymmetnd
3 Boiling point Mo
1BaeedomVauderWa.d
forces
4 Thermal Legg More
stability
5 Heat of More Legg
Hydrogenation
6 solubility in
H2O Mosef
d A Give the total number peeeibleieomess for
the compound with molecular formula GFUBRI

9.2 Which of the following compounds can show

geometrical ieomeriem Give the total member
of geometrical ieomerspeceible for those
compounds and draw their configurations
is Icty dtdb

Ciii CD
csy atdb

k k
d ctz CD dtdb
f f
R 912 4,91913
vii d
a ice
Q K
Ith at ab
f f
 Optical Isomerism
Configurational ieomerism in which the two isomers
how different behaviour towards plane polarised
light is called optical ieomen em and the ieomess
are called optical ieomorco.IS ofeach other
A A
4 D D D
a D
p
General Nicole plane poolarieed
effhitet Prism eight PD
npolarieed Oscillation electric
of
Oscillation of electric and magnetic vectors
and magneticvectors in in any one direction
all directione
For optical ieomers A B C D
If PPL is passed
through their aqueous solutions and following
ob
aremadeervations
A se No change in planeof oscillation
D
Plane oscillation changesby
B of
a Oa
of
a
angle in anticlockwisedirection
Plane
C
se of oscillation changes
a
by 0 angle inclockwise
direction
D se Plane of oscillation
o
changes by Ozangle
in either direction
 optically inactive while
is are
optically active but all are 0.7 of each other
2 are Enantiomers of each other three
are non superimpoeible mirror images ofeachother
is optical diaetereomer all
3
of
ie neither mirror image nor superimpoeible
4 MixtureofBO is called racemic mixture
If it is equimolar mixture it will not how
optical activity due to intermolecularcoup
eneation of rotation
Thug racemic mixture are mixture of enantiomers
in which each compound is optically active but
the complete mixture show bag or no optical
activity
Racemieation formationofracemic mixture
Optical Reeolution Doniganice a EnamnfEmers

S A is Meeo compound which shows optical inactivity

due to intra molecular compensationofrotation
This is because compound TA is symmetrical i e
achiral Have plane of symmetry in it
6 Compounds B C D are chiral i e a gym
metric which can be due to pretence of
chiral or asymmetric C atom or
without it
7 All optical homers are always non gyperimpeeible
oneach other but they can be mirror images of
each otherLeg Enantiomers or can't be minor
im ges
of each other e.g Diastercomeered
Measurement of Optical Activity
1. Angle of Rotation (0)
Total angle by which plane of oscillation ofPPL
is changed by any octical ieomer optically act
ive ieomer is called its angleofrotation
factors affecting Angleof Rotation are
I Nature of atoms or groups in it
2 Wavelength of PPL cued in experiment d
3 TemperatureCD
4 Concentration ofsolution
S Length
of polarimeter tube
2. Specific Rotation (A )
Angle ofrotation underspecific conditions It is
calculated expened ae

o
I C x e
Here D Definite wavelength
To 298k 25 Roomtemp
C I g me l Pathlengthdm
 Note
specific rotation is definite for a given optical
ieomer but its angle of rotation may change
Thug optical activity of optical ieomers is compared
in terms
of their specific rotation rather than
total angle ofnotation
3. Optical Purity
It gives percentage of any pure enantiomer in
an enantiomeric mixture It is calculated ae

OpticalPurity Observed OpticalRotation

Optical Rotation ofPureenantiomer

Racemic Mixture too OpticalPurity

3. Enantiomeric Excess
Itgives percentage excas of any one enantiomer
in enantiomeric mixture
EnantiomericMixture Cd e Xaoo
Cdte
Note
Numerical value of optical purity
and enantiomeric exam for a
given enantiomeric mixture is
same but conceptually they
are different
 e.g Q Give the optical purity enantiomeric
of an
mixture with total rotation of 8 29 If
specific rotation of one of the enantiomer is
found to be 17.2
solution Opticalpurity too 4 66
Out of soo molecules 47.66 are pure
enantiomer while reet 52.34 are racemic
mixture i e having 26.17 unit of each
enantiomer
Thus D 47.66 26.17 73.83
and he 26.17

Thug enantiomeric excell 73.83

22617 too
73 83 126.17

47.66 Chore
Types of Optical Isomers
(A) Enantiomer ;

Optical ieomers which are non superinpoeible minor

images of each other are called enantiomer
Note
C Enantiomers always exist in pair
Enantiomers are always optically
active and shows equal specific
notation in opposite direction
 Ciii Two enantiomer are always chiral compound
If enantiomers have chiral C the configuration
around each and every chiral C atom is always
oppeeite
(B) Optical Diastereomers ;
Optical ieomers which are neither minor images
ofeach other nor superimpoeible on each other
are called optical diastereomer
Note
is There can be two or more diastereomer of a
compound
Diastereomors may or may not be optically
active
Ciii Optically inactive diastercomers are called Mao
compound which show optical inactivitydue
to intramolecular compenealioy ofrotation
im arted
by plane ofsymmetryin it
Diastereo mess always have different magnitude
of specific rotation that can be in game or
opposite direction
Note
Magnitude ofspecific rotation depends
upon type of atoms bonded to chiral
and direction on their configuration
 Chiral or Asymmetric Carbon
carbon atoms directly bonded to four different
atoms or groups It is represented by It
Note
Different ieotopes of game element are also
treated as different atome
COO n fo OH
e CR H
molten chiral c GEN Hz
try M
Amino Acid
Projection Formula of Configurational Isomers
Most commonly cured projection formula for

1 Dash
con igurational
Ieo mess are
Wedge diagram
2 Fischer
projection
3 Haworth projection
Fischer Bojection
This is a method of representing 3D structure of
a compound in equivalent 20 form by following
definite set ofsales
Compoundis observed in a
way that all
the atoms and groups bonded to chisel C
lies on vertical and horizontal
polition Now keeping vertical groups
 ay fro
All the atoms bonded to chiral Case placed
on same plane on vertical and horizontal
politione only
Cii Is general C chain is placed in vertical
position with mostoxidieed C atom on top
Absolute Configurations around Chiral Carbon
(R, S System of Naming)
For aeeigning absolute configuration around any
chiral C all the four atoms or groups bonded
to it are numbered
from a ton on priority
balis as given by C.I.P melee
Now absolute configuration is aeeigned by observing
the direction of rotation from a 2 3 01 as
followe
In Dash wedgeFoom In Fischer Projection
tf
Rotatiopfsitiophn.fm
9TH Close Vertical Horizontal
froma 2 a
Away
Clockwise R B R D
r I r l r i r
Anticlockwise S R S R
Note
R Rectus_Right S sinister_Left are too
opposite configuration offour atoms orgroups
around a chiral C and doesn't stand
for direction of optical rotation of
compound
d 3 Give R s configurationaround chirale of following
compounds and classify them into identical and
enantiomers
Ab OM
is
fine
9 A
on H
1
a
h Bc
H 9
H I
c

Eez
non not ay H

Ce ay
Citi Mo
ESH n on
CyCB
ce
Ce M
d H Br da
BY I
I g
ay ay
c A Coon a n

H COOH

ay ay
i a Coon a n

H COOH
 Relative Configurations around Chiral Carbon
(D, L-System of Naming)
It was introduced by fischer
for this purpose the correct fischer projection
fo mula
of any compound having chiral C is compared
with fiecher projection formula of two enantiomers
of Glyceraldehyde ceylon EtCon Cleo
Ho Cho

H Eton Ho CEH
3910M ALON
2R C 22S
D L

2,3 Dihydroxypropanal
compounds having configuration around last chiral C
like D glyceraldehyde are aeeigned D configuration
and those having configuration like Lglyceraldehyde
are aeeigned L configuration
Note
D glyceraldehyde is dextrorotatoryED
but all compoundshaving D configuration
are not dextrorotatory Similarity.L
glyceraldehyde is laevorotatory but
all Lconfigurations are not
d4 Give the correct D L configuration of following
structured
ay ay ay
C MO Coon no Coon Ciii Ho n
H H COOH
Ctg Oh HHz
cymo n d Hate
ESH Ia
2
coom cry MOOC OEM
ay
ab M
Cii d 00h
Ciii Ear
µ lf Be titty
COOH
H
Elements of Symmetry
symmetry similar or equal distribution
Elements of Symmetry
I
Centre of Symmetry Axis of Symmetry Plane of Symmetry
(CoS) (AoS (PoS)
Anycentrepoint in astra Anyimaginary line drawn
cturethrough which when throughanystructurearound
Any imaginary plane
drawnthrocy a structure
astraight line iepaeeed.in which when the structure whichdivides it into
any direction ittouch game isrotated 360 the same equalhalf ohichappear
byobserved
arrangement ateguddietance appearance is more to beminorimages
in two oppositedirection thanone time on observing eachother
Note Anystructure canhave foomeamepoeition The of
iscalledPos
only one cosand that too number same observati
at its bodycentre ones in one complete
rot tion
gives the typefoldof
Axisofsymmetry AOS

d 5 Give number Cos Aos Ipos

of
 in following compounds
d Methane
Cii Eclipsed conformation of ethane
staggered conformation of ethane
I fully eclipsed conformation of n Butane G G
c Anti staggered conformation of n Butane G
Cyclopropane
Cii Methylcyclopropane
Qin Cis d 2 Dimethylcyclopropane
CX Trans d 2 Dimethylcyclopropane
Cyclobutane
i Cie q2 Dimethylcyclebutane
DTrans q2 Dimethylcyclesbutane
Xiii Cia I3 Dimethylcyclesbutane
Xiv Trans E3 Dimethylcyclobutane
Answers
Optical Isomerism in Compounds with Single Chiral Carbon
Around any chiral C these are two different preeeible
configuration giving tooo non superimpoeible minor
images which are two optical ieomorg
eg Tn lactic acid
ay Inn oooh
2 Hydroxypropanoicacid
In dash wedge diagram
s
2 2
i 2900ha on
goon a et go go
h
h
that i
in 9th
BETi I DIN
By
i g lI 9
ER 3 BO
COOH COOH
i
Z H OH no µ

CHG CHz

Trees
forcompounds with single chiral C
A Humber
of total optical ieomess 2
2 Numberof optically active ieomers 2
3 Number of optically inactiveneedforme0
4 Number of enantiomericpairs a
S Number diagtercomeric peeing o
of
 Optical Isomerism in Compounds with Two Chiral Carbon
(A) With two equivalent Chiral-C

e.g Tartaric acid 2,3Dihydroxybutanedioicacid

Coon 1 Coon Coon 1 COOM
H OH 1I no H H OH THO
I
H
M OH
quo
H Ho H
I H on
COOH COOH COOH COOH
Pos AO
ER GR 3R
IS 3R 26,35
Identical Enantiomers
Optically inactivelmeso optically active
Note Eclipsed
cook staggered
COOH
Newman
coom
OH M 0h
H OH Oh
i
My COON
M OH
on
coon Feige EEh
H I M Yoon
Ho on µn
Trees compounds with two equivalent chiral C
for
1 Humber total optical ieomess 3
2 Number
of optically active ieomorg 2
3 Number of optically inactivelneedformed
4 Number of enantiomericpairs _I
5 Number diastercomeric peeing _2
of
 (B) With two non-equivalent Chiral-C

e.g 2,3 Dihydroxy pentane

CHz I CHz CHz I CHz
H OH THO H H OH THO H
M OH no H Ho H H OH
I 1
GHS GHS cuts GHS

IS 3R CER 3S 45,35 GR 3R
Enantiomers Enantiomers
optically active optically active
Eclipsed staggered
Note cries Ctb
ay Ho H
Newman
ay
H OH 80h4 m on
MH
OHfjfgeh
GH ans
M
9E dans EEh
n A m fg GHS
n.sn
no 0h

Trees compounds with two nonequivalent chiral C

for
A Humber total optical ieomest 4
2 Numberof optically active ieomen 4
3 Number of optically inactivelneedformeo
4 Number of enantiomericpairs _2
5 Number diagtercomeric peeing _4
of
 Optical Isomerism in Compounds with >2 Chiral Carbon
(A) With Different ends

Total Optical ieomerg _2h

A No of chiral C Optical centre
Note All are optically active
I Homelo compound is formed
(B) With Similar ends

Total optical ieomers 2h

Became me compounds are aleo formed
offPImptotineddisotinder OpticallyActive OpticallyInactivenessTotalOpticalIsomer EnantiomericPair

I Unsymmetrical
ends 2h O 2h 21
2
2 Symemnedftical
fate zen23 2 za1,2kHz EE
CWitheven noof
Catoms
Withodd no of zcnIIznctyzz.NET z zaD 2412K
Catoms 2

Here Number of optical centre Chiral C

n
c9I dnh d9H a80pticalieomor
e.g t.az ag No meee compound
Optical ieomer
y 9µ_cµj
49M
2 C cuz 2 Melo compound

419 dah 4 Optical isomer

dDay guys 2 Melo compound
of
Pseudochiral C
 Pseudo Chiral Carbon
C atom chirality depends upon absolute
where
configuration of other chiral Cinthe compound
are called pseudo chiral C
i ab
e.g AB s ay ay
U M Q u H
M g i H
ice n a a H
n a H H Cl
H et
g f G et
H A H
I
CHz y CHz Cfb y CHS

EEESR.IR sf2G4s7C2R
4 peetudoaggymetrie Enantiomers
Identical Meeee
Pg is called pseudo chirale ie c atom
whose chirality depends upon the absolute
configuration Gotherchizal carbons
prevent in the compound
Optical Isomerism in Compounds without Chiral Carbon
Allen es ith even no of double bonds
Spiranes with even no of rings
Substituted biphenyls co substituted
Amina Quaternary amine salted
Note
In allenes cummulatedpolyenes and spiranes
with even number of double bonds and rings
repectively the two ends becomes nonplanar
They can show optical ieomorieutenantiomorieng
the atoms on each end are
if or
groups
different though the atoms or groups at
two different ends can be same
e
g n nee
c
I c c M
c

U
I X n il nI ke

Honsuperimpoeible mirror image

Enantiomer
4 mince I M
I X n il nI 4 ee
U
d
Cii Biphenyl have coplanar rings
H H

H
Maximum
a Number of total atones on a plane 22
2 Number carbon atones on a plane 12
of
3 Number
of hydrogen atoms on a plane _to
h Number of total atones on an axie G
S Number of carbon atones on an axie 4
6 Number of hydrogen atoms on axis 2

Substituting o H on both the rings by other

atoms or groups cause bees of planarity due
to steric effect of the group If the two
ortho positions of each benzene ring is
substituted by different atoms or groups
compound becomes chiral and shows optical
ieonrenism enantiomericnd

EE E
Honsuperimpoeible mirror image
Enantiomer
 Ciii In amineswith three different atoms
or groups attached to H atom acts
as chiral centre But two configurations
around it changes into each other through
in version of groups thus making the
two forms non ieolable
e.g Inversion in Amine
ay
B9µ I MM
H
I Det
Et
In quaternary amine ealt the inversion
around H atom is checked thus if H is
bonded to four different atoms or groups

it shoves eerautiioynesiem
e.g k 0
r I EINB
RIEN i
Ry Ku
Hansuperimpoeible mirror image
Enantiomer
0 I
Note 11 a

Hatem FIH HII

Tertiary
doesn't show inversion due to cyclic
structure they can show enantiomers'em
 Conformational Isomerism
Conformations

Different 3 D structure of compound obtained

a

by free rotation of one

part of any compound
w r t another
part of compound around any E d
single bond axis are called conformations
Thug conformations are different spatial arrangement
ofatoms or groups obtained byrotation or twisting
of the bond6 in a compound
Note
Different conformations of a compound havevery
small difference in the potential energy and
thug stability Estability A trot Energy
CD Conformational Energy The rotational energy barrier
between Moet and least stable conformations
is called conformational Energy
It depends upon following strains ie increase
in potentialenergy cauling descale instability
Citi Types of Strain
1. Angle Strain It arises due to deviation of bondangles
from normal value It is common in cyclic
compounds but not in acyclic compounds
2. Torsional Strain It ariees due to repulsion

between bond pairs of e a present

on adjacent atome
 It is aleo called Pitzer or Eclipsing strain
3. Steric Strain It arises due to Van der Waalsepuleion

of atoms and groups preeent on adjacentatom

Allo called Van der Waal strain
Compounds Bond Angles Angle strain
I Cyclopropane

2 Cyclobutane
3 Cyclopentane

4 Cyclohexane
Conformers or Conformational or Rotational Isomers
Different
conformationsat potential energyminima are
called conformers or conformational deomerg
or Rotational isomer
Dihedral Angle
Apparent angle between two bonds
present on different atoms whey molecule is
observed along any o bond axis in the compound
is called Dihedralangle

Important conformations to be studied

are I Ethane Propane ButaneCCI G'axis
2 Butane ez Cj axie Ethyleneglycol
3 Cyclohexane Methyl
cycl hexane
 Conformations of Ethane
skewer
Eclipsed Gauche staggered
q
sawhorse n th n
projection 41 Ete
h H
68
soo
a
off
n HIMn
Hh
1 Hydiahedsq
Newman's 68 a ly HH
projection th p 60 M H

Eclipsed Skayoanche staggered

stem
strain Maximum Intermediate Minimum
Torsional
strain 1 Maximum Intermediate Minimum
Potential
Energy Maximum Intermediate Minimum
Stability Minimum Intermediate Maximum
PE
A
Eclipsed
12.510kcal

staggered

D
Dihedral 0 60 0 68 0 600 00
angle
Total 0 600 120 180 240 300 360
rotation
Note Conformations of propane and butane
7
along around G G'o bond axis are
similar with 14.5219 KTmoticorfenergy
 Conformations of Butane around C’—C’
2 3
Bond Axis

93 ats
abMuy
d 9
ab T arts
d
Hrh
Kenan
HI HI hi HIEntry Hi
9
ab
n n n n
fully Gauche partially Anti
eclipsed Cstaggesed eclipsed Cstaggered
Bong Ctb BCH Ctg
1 H Ab I M H

th p n n th H H
M Hy ay
Chiralform
Stefan Higheet Lower Higher Lowest
Torsional Low Low
strain High High
Potential Lowest
Energy
Highest Lower Higher
stability Loweet Higher Lower Highest
 Note
Two gauche conformations of n butane are
confo mational
enantiomer while they aleo are
confo mational
diastercomer of Anti conformation
Effect of H-Bonding on Stability of Conformations
Presenceof intramolecular H bonding increases the
stability of conformation
e.g In ethylene glycol Ho 942 CHEON

on 10h OHM OH OH Y OHM H

Kenan d 9 denson d f
tf n tf th
n
tf n tf 1 OH
n n n
fully staggered partially Anti
eclipsed Gaudhed eclipsed staggered
noon 0M HoH OH
I ly OM I ly H
th p n n th noth n n
M OH

Most stable
due to intra
molecular
Note HBonding
Intramolecular H bonding is shown by
all the compounds having HOCHECHEA
type formula Where A'can be f
OH MHz NHR
 Conformations of Cyclohexane

Boatform chairform
fflagpoley Hq
He the He Y9 the e

Ee Ee µe Ha
Hastie
HedHa Haste eh 14 tea

Ha Ha Ha
Eclipsed form staggesedfoom
Legg stable Duet more stable
C stericstrainbloflagpoleHs
Torsionalstrainbloaxial Hg Ha
HH H9 Hq
eH He
He
en eHµe EH He
Ha Ha
Hmg Mta
a
Hq
a
Note
C Cyclohexane exists in two chair forms which are
converted in each other
by inversion ringfipping
which need 45k Mott activation
Ma
energy at 25 C
Hz
Hz Ek LkH2 th th
H innZ
d I
Mand n HAHA
2 I HZ Hd A
Hd Hz Hd Hz
Hy Hz
Cii
Inversionorring flipping changes axial Hs into
equatorial and vice versa
Ciii Different conformation formed between
two chair forms are
Half chair Least stable
Twietboat It is chiral
True boat
Potential energy change during oing flipping is
given as follows
fE a Karol 1 Molecules
43
in
Twistboat 21 I
Chair O 99
D

d Geometrical ieomeriemin substituted cyclohexane

RelativePosit a a a e
Porition
ionoggroup or or
mofffterming e e e a

Adjacent Trans Cig

Odd even

Alternate
CBrothgren Cig Trang
Bothodd
 is In many cyclic compounds boat form becomes
stable due to intramolecular H Bonding
e H Bonding
g
H o µ
H H H E
E E

H
HoH SH
H H

Cii In methylcyclohexane methylgroup present

at equatorial position imparts more stability
due to lower stork strain than at axial
position
H M
K EN
mu n
th th M
H H
hah n na n
n H d M n H H
H M
h IIn h
Equatorial Me
Axial Me