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Stereo Chemistry Notes
Stereo Chemistry Notes
GENESIS TUTORIALS
Stereochemistry
Elements of symmetry:-
(1) Axis of symmetry:- (Cn)→ Imaginary axis passes through the centre of the molecule
called axis of symmetry, highest order of the axis of symmetry called principle axis,
remaining axis is subsidiary axis.
Example:-
(2) Plane of symmetry:- (𝜎) → Any molecule having 3 types of possible plane—
A centre of symmetry is a point with in a molecule such that if an atom is joint to it and the
line plotted to an equal distance beyond, it incounters an equivalent atoms or point.
Order of priority– I > Br > Cl > F (On the basis of atomic number)
(iii) Priority gives according to atomic number but in case of isotopes priority assign on the
basis of atomic mass.
In case of carbohydrate, if the OH group will be right then configuration is [R] and OH is in
left then [S].
(1)
(2)
(3)
(4)
(6)
(7)
(1)
(2)
* Relative configurations:-
(1)
(2)
Optical Activity: The compounds having the ability to rotate the plane of polarized
light (PPL) are called optically active (Chiral) compounds. This phenomenon is
known as Optical Activity (Chirality)
* CHIRALITY
Types of Chirality
(i) Allenes
(ii) Biphenyls
Allenes:- H2 C = C = CH2
HC = C = CH — Commulatated doublebond
Structure of Allenes:-
If number of double bonds (2,4,6,8) (even) than terminal bond are present in the perpendicular
plane.
Odd number of double bonds (1,3,5,7) then terminal bonds are perpendicular to the plane
present in same.
(1)
(2)
(3)
Note:-
This type of molecule doe not show axial chirality because terminal carbon not lie in Cz axis
Example-1
Example-2
Example-3
Example-4
BIPHENYLS:-
(1) Proper substitution i.e. both ortho position of each benzene ring must have 2 different
ligands.
(2) Ristriction of rotation or stable configuration that is O-substituent must be bulkyl group
which is restricted rotation.
It has been found that if a substituent present at m-position of benzene ring in biphenyl the
energy pf activation for recimization is enhance this is know as bulteresing effect of m-group.
Bultersing order(m-substituent)
Briged Biphenyls:-
if n = 2,3 — chiral
(1) Ansa-compounds:-
(2) Paracyclophane:-
(3) Trans-cyclootences:-
(4) Helicity:-
(ii) For helicity if the substituent are present then minimum have 3 in angular fashion.
P(+) → Clockwise
Note:- For prediction of P/M i.e. configuration in hedical structure, we strict from above to
below [M].
* Organometallic compounds
Example-1.
Example-2.
Example-3.
Types of Stereoisomers:-
(a) Enantiomers (Relative):- Those molecules which are non-superimpose mirror image
with each other are known as enantiomer & this property is known enantiomers.
Example:-
(1)
Note:-
* exo-exo — enantiomer
* endo-endo — enantiomer
* Propertied of enantiomers:-
(1) They have same physical properties such as melting point, boiling point density refractive
index, but they show different behaviour towards plan polarized light.
A = [𝛼] = -20°
B = [𝛼] = +20°
(3) The isomer which rotate parallel in clockwise direction called dextro rotatry (d, (+)) and the
isomer which rotate parallel anti clockwise rotation called levorotatory ((-), l).
(4) They have same chemical properties in achiral medium but they have different chemical
properties in chiral medium.
Enantiomers can’t be distinguished by H-NMR system in achiral medium (solvent) but they
can be distinguished in chiral medium.
* Diatereomers:- Those molecule which are not mirror image of each other is called
diastereomers. They may or may not be chiral that is may or may not be optically active.
Cis trans & E/Z nomenclature are always diastoreomers.
* How to identify?
No of centre A B
1 R S → No vesbe diastereomers.
2 RR RS → diastereomers
3 RSS RSR → diastereomers.
Note:-
Exo-endo Distereomers
Endo-exo
Meso compounds:- Compounds having more than 1 chiral centre but optically inactive due
to presence of plane of symmetry are inversion centre are known as meso compounds.
Solution
(S)-3-(prop-2-enyl)hex-5-ynoic acid
N having trivalent (three group are different) and lone pair should be optically active but
due to umberalla inversion or pyramidal inversion it becomes optically inactive
(Recemization takes place)
* Prochirality:-
Prochiral centre:- A centre at which a single substitution makes centre chirality called
prochiral centre.
* Pro stereogenic centre:- A centre at which a single substitution by a new ligand gives a
new stereogenic centre called pro stereogenic centre.
TOPICITY:- Stereo chemical relationship between two or more ligand within a molecule is
defined in terms of topicity.
Stereogenic centre:- A stereogenic centre is like a umbrella term under which a chiral
centre is defined. A stereogenic centre is just a location in a molecule where the interchange
of any two group gives a new stereoisomers.
On the basis of stereochemical relationship ligands of phases are classified in the following
ways.
(1) Homotopic ligand:- Two ligand are said to be homotopic if they are replaces by new
ligand (achiral) gives a pair of two products which are identical or homomers to each other.
Two ligands are said to be hetrotopic if they are replaced by in turn by new ligands (chiral)
gives two enantiomers
Compounds having diastriotopic ligands may or may not be chiral in the case of geometrical
isomerism (achiral) but optical compounds are optically active.
Note:- Geometrical isomers (cis-tran/E-Z) are always diastereoromers with each optically
inactive.
Question.In the gcompound given below, the realtion between HA, HB, and between Br1, Br2
is:
(d) HA, HB are enantiotropic; and Br1, Br2are homotopic[NET Dec 2012]
(iii) Diastriotopic ligands are not interchange by any symmetry elements (Cn , 𝑖, Sn absent)
Solution. (c)
[JAM 2016]
Solution.(b)
Solution. (c)-3
TOPICITY IN FACES
(1)Homotopic face:-
(2)Enantiotopic face:- Faces of the double bond are said to be enantiotopic if the compound
will be achiral and addition on the faces produce enatiomers. Such type of faces is called
enantiotopic face.
* Diastereotopic phase:- Faces of double bonds are said to be diastereotopic if the addition
of Nu+ in term to form chiral or achiral to produces diastereomeric diasteretopic with
each other called diastereotopic faces.
Note:- (I) For Pro-R & Pro-S configuration newly incoming ligand always give 3rd priority
(II) If incoming ligand priority order is higher than that case substitution takes place by
smaller groups like deuterium.
NOTE:- In Re and Si nomenclature, Ist priority always gives oxygen and then according
* Calculation of stereoisomers:-
(1) Stereoisomers having n-chiral and have no σ1 , i, Sn in any all possible stereoisomer i.e all
stereoisomers are chiral then number of stereoisomers is equal to 2n
(2) Stereoisomer having n-chiral center and have 𝜎 plane in at least one of the all possible
stereoisomers.
(i) if n = even
The isomers which rotate perpendicular in clock wise direaction are called dexto (d) or (+)
like wise perpendicular rotate anticlock wise are called levol or (-) d and l and isomers or (+)
& (-) are enatiomers to each other.
Note:- d/l isomers can’t be identify not the basis of their configuration it is the polarimetry
which help us to identify d/l isomers.
* PPL:-
In PPL E.M.R waves oscillate in a single plane perpendicular to the direction of propogation.
It is the angle of rotation of plane polarized light (PPL) passing through a chiral medium in
polarimeter tube is known as optical rotation.
𝛼 ∝ 𝐶𝑙
𝛼 = [𝛼]𝜆𝑇 C.l
l = 1dm → 10 cm
If c = 1gm/cm3 or l = 1dm
𝜶 = [𝜶]𝑻𝝀
SPECIFIC ROTATION:- optical rotation (𝜶) of plane polarized light (PPL) passing through
1 g/mL concentration solution of a chiral molecule in a tube of 1 dm length is known as
specific rotation, represented by [𝛼]𝜆𝑇 .
An optically pure organic compound having molecule unit 200 was analyzed by a
measurement of its specific rotation and 2 molar solution of this compound shows +3.5° at
1dm length. Calculate the specific rotation.
2n
Concentration 2M = V
400 3.5 ×5
= 1000 = = 8.75 degree gm−1 ml dm−1
2 ×1
When 20 miligm organic compound in 1cm3 tube iof ethanol and solution places in 10 cm
long polarizer cell and optical rotation 𝛼 = -4.35° measured at 20°C with wavelength of 589
nm. Specific rotation of the compound.
20 1
20 milligm = 1000 = 50
1
1
C= 50
=C=
mL 50
−4.35 ×50
[𝛼]𝑇𝜆 =
×.1
[𝜶]𝑻𝝀 = 217.5
(ii) A solution containing equal amounts of both enantiomers are said to be optically inactive
and called racemization.
(iii) When a solution containing unequal amounts of enantiomers then the form optical purity
or enantiomeric excess are used with respect to any enantiomer.
α mix
ee = × 100%
α pure
* %d + % l = 100
%𝑑 = 100 − %𝑙
[𝑑−𝑙]
* 𝑒𝑒 = [𝑑+𝑙]
× 100%
R−S
* ee = R+S
× 100%
* A mixture two enantiomers shows optical rotation + 12°. If the specific rotation is 32°
calculate the composition of enantiomers?
α pure = 32°
12
e.e = 32 × 100%
𝑙 % = 31.25 %
31.25 + 37.5
Total d = 68.75 %
Question. (+) Mandelic acid has a specific rotation of +158º. What would be the observed
specific rotation of 25% (-)-mandelic acid and 75% (+)-mandelic acid? [DU 2016]
α mix
ee = × 100%
α pure
α mix
50 = × 100%
158
50 ×158
= = +79°
100
Question.The rotation of pure R(+)-Limonene is +123.0º. Calculate the % of the (+) isomer in
a sample showing a rotation of +109º? [UOH 2011]
α mix
ee = × 100%
α pure
109
ee = × 100%
123
ee = 88.6%
This will be obtained by (94.3-5.7 = 88.6 ). It means that 94.3% (+) isomer and 5.7% of (-_
isomer are present in sample
(c) option
Questionthe specific rotation [α]D for (S)–(+)–2–butanol is 10° mL/g dm. The observed optical
rotation (αabs ) of a sample composed of a mixture of (R)- and (S)-2-butanol is -0.45°. If the
cell path length is 0.6 dm and the concentration of 2-butanol in the sample is 0.15 g/mL,
the percentage of (R) and (S) enantiomers in the sample are [NET June 2017]
(a) (R) = 25%, (S) = 75% (b) (R) = 40%, (S) = 60%
(c) (R) = 60%, (S) = 40% (d) (R) = 75%, (S) = 25%
l = 0.6 dm
−0.45 −5°
[α]Tλ = 0.6 ×0.15 = -5° ee = 10
Solution: Optical purity also known as ee of a compound of 90% show +135° specific rotations
135
So, its 100% pure optical isomer will show = × 100 = 150° specific rotation
90
120
At 1 hors the specific rotation reduces to +120°, so the ee or optical purity = 150 ×
100
CYCLOHEXANE
Answer (b)
Cyclohexane exists in different form but chair form is most stable form
Stability order:-
In half chair angular strain is present as well as eclipsing effect is also present that’s why half
chair is most constable.
In twist boat form eclipsing effect and 1,4-flag pole repulsive, interaction decrease in the twist
boat conformation.
NOTE:- Generally in chair form equatorial substituted group cyclohexane is more stable.
Question Ring flipping of the compound in the following conformation leads to [GATE-2016]
Solution
[a = axial; e = equatorial]
Answer is (c)
Question. The increasing order of energy of the following conformers is: [UOH 2016]
(a) (II) < (III) < (I) (b) (I) < (II) < (III) (c) (III) < (II) < (I) (d) (I) < (III) < (II)
I – Half chair
II – Twist boat
CYCLOHEXANE DERIVATIVE:-
Question. The configuration at the two srerocentres in the compound given below are
Solution.
Solution
* ANOMERIC EFFECT:-
(ii) Presence of electronegative group at Anomeric carbon must lies at axial position to give
most stable structure/conformer.
Group or Atom X. lipe -OH, -OMe, -COR, -Cl, -Br, NH-R, etc.
* DIMETHOXY METHANE
CONFORMATIONAL ANALYSIS:-
If two different 3-D arrangement of a molecule are inter convertible into each other nearly by
free rotation about single bond are called conformer.
* Conversion of one conformer into another depends on energy barrier if the energy barrier is
small that can be achieved at ambient temperature conformer remain in a rapid
equilibrium.
STRAIN IN CONFORMER
(1) Torsional strain:- it is a repulsive force which operates between co-valent e–(s) (covalent
bond) of two vicinal atoms in eclipsed conformation.
X Y
H H 1 Kcol/mol
M Me 1.4
Me Me 3.4 – 3.6
Et Et 3.7-3.8
(2) Angle strain:- (Beyer strain):- This type of strain is found in cyclic molecule any
deviation form normal sp3 bond-angle 109° 28′
1
d = 2 [109° 28′ - θ]
1
(1) Cyclopropane - ∆/ = 2 [109° 28’ - 60]
d = 24°44′
1
* Derivation ∝ stability
X Y
H H 0.00
Me H 0.00
Me Me 0.9 Kcol/mol
Et Et ≤ 0.9 ≈(1) Kcal/mol
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* Dihederal Angle:- [𝜃] → It is defined as angle between two bisecting planes of two bonds
present at vicinal carbon atom.
It is non-directional in nature i.e it does not tall anything about the direction of rotation of
single bond in conformer
* CONFORMATION OF n-Butane
Potential Energy Diagram for this stability I > III > II > IV
Question.Given the energy of each gauche butane interaction is 0.9 kcal/mol, ∆G value of the
following reaction is [NET Dec 2012]
(a) 0.9 kcal/mol (b) 1.8 kcal/mol (c) 2.7 kcal/mol (d) 3.6 kcal/mol
Solution
(a) plane of symmetry; and is achiral (b) C2-axis of symmetry: and is chiral
(c) centre of symmetry; and is achiral (d) plane of symmetry; and is chiral
Solution.
* IN GASEOUS PHASE
* (Interaction → repulsion)
Rule- Bridge head carbon cannot be sp2 hybridized unless ring size is large enough.
Cause:- Bridgehead and adjacent carbon both are orthogonal to each other that’s why proper
overlapping not tales place.
Example
Application:-
(i) Stability of 𝐂
c>b>a
Stability increase
Anti-Bredts Rule:-
Cram’s Rule
In the addition reaction of carbonyl compounds having chiral center at adjacent carbon
distereomeric product which one of the distereomers could be predicted following rules:-
(i) Draw the Newmann projection of chiral carbonyl compounds placing bulkiest (large) anti to
carbonyl group
Trick
(1) Chiral carbonyl compounds having EWG do not follows cram’s such type of reaction can be
predicted by dipole cram’s rule
(2) If hetroatom like oxygen, Nitrogen, sulpher are present at chiral centre of carbonyl
compound cram’s rule may be wrong information.
(3) Although cram’s rule predict the stereo chemical relation but if fails to explain the
Quantitive assessment of asymmetric induction in form of steric interaction.
Felkin-Anti Model:- According to this model the most stable conformation of carbonyl
compounds having chiral centre at adjacent atom are those in which the large
group/heteroatom non-chelating condition is perpendicular to the carbonyl group.
𝐌𝐠 𝟐+
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𝐙𝐧+𝟐 Chelating
𝐓𝐢𝟑+
If Reagent having chelating (like Mg2+, Ti3+, Zn2+ etc) & carbonyl compound having hetroatom
at chiral centre than that condition large group (hetro group) will be perpendicular to
carbonyl.
(*) If large group is parallel to C = O then stereo of incoming group will be same as smaller
group stereo.
(*)If large group (hetro atom) is perpendicular to C = O then the, stereo of incoming Nu + will
be same as medium group stereo.
(3) If two same group present in same side then this is called cis and another will be
trans.
When any alkene having three different group then in that condition cis-trans not applied
that type of molecule we introduce E/Z nomenclature
E = Anti = Trans
Z = Zusaman = cis
STRUCTURAL ISOMERISM:-
The compounds having same molecular formula but different structure that is different
arrangement of atoms or group molecule within the molecule are called structural isomers,
thephenomenon is called structural isomerism.
Chain isomerism:- The compound having some molecule formula but different arrangement
of C-chain (skeleton) with the molecule are called chain isomers, and the phenomenon is
called chain isomerism.
𝐂𝟓 𝐇𝟏𝟐
𝐂𝟒 𝐇𝟏𝟎 𝐎
𝐂𝟒 𝐇 𝟖
Position isomerism:-
Compounds which have same Molecular formula but different in the position of functional
groups.
METAMERISM
The compound having same molecular formula but different number of carbon atoms or
alkyl group on either side of the functional group are called metamers
TAUTOMERS:-
This is a special type of functional isomerism in which the isomers differ in the
arrangement of atoms but they exist in dynamic equilibrium which each other.
(1)
(2)