Stereo Chemistry Notes

44-Karanpur, Near Luxmi Narayan Mandir, Dehradun
Contact: 8171000425, 7252022576

Web: www.genesis-tutorials.com
Email: [email protected]
GENESIS TUTORIALS
Institute for CSIR-UGC-NET/JRF, GATE & IIT-JAM
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—
(1) σv – vertical plane– plane parallel to principle axis.
(2) σh – Horizontal plane or molecular plane.
(3) σd – Dihydral plane (operation reflexion).
σh – plane perpendicular to principle axis.
σd – place bisect two Cz angle.
(3) Inversion centre (centre of symmetry):- (i) operation–inversion
Note:- i present → optically inactive compound
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.
(4) Improper axis of symmetry (Sn):- (Operation – Roto-reflexion)
Rotation followed by reflexion in a plane perpendicular to the axis generate a structure

indistinguishable from the original.
Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 1

Contact: 8171000425, 7252022576
(5) Indentity (𝜺) – (operation-nothing to do)
* CIP Rules:- (Cahn-Inglod-Prelog):-
Order of priority– I > Br > Cl > F (On the basis of atomic number)
Assign priority of the different substituents accordingly.
(i) Lowest priority group must away from observer.
(ii) Rotates the eye with decreasing order of priority.
(iii) Priority gives according to atomic number but in case of isotopes priority assign on the
basis of atomic mass.
Note:- RS nomenclature always gives chiral molecule

Contact: 8171000425, 7252022576
Fisher representation:- (2-D) [R]
In case of carbohydrate, if the OH group will be right then configuration is [R] and OH is in
left then [S].
* Mesotartic acid is optically inactive due to internal compensation
(1)

Contact: 8171000425, 7252022576
(2)
(3)
(4)
(5) Note:- Fisher representation always show eclipsed form.
(6)

Contact: 8171000425, 7252022576
(7)

Contact: 8171000425, 7252022576
* Saw-horse projection formula
(1)
(2)

Contact: 8171000425, 7252022576
* Relative configurations:-
(1)
(2)
Serine is the standard of amine which is—
→ All amino acids having S configuration except cystein
→ Generally relative configuration used in carbohydrates and amino acids
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

Contact: 8171000425, 7252022576
(i) Axial chirality:- Axial chirality show following compounds— [ABS]
(i) Allenes
(ii) Biphenyls
(iii) Spyraives (spiranes)
Allenes:- H2 C = C = CH2
CH2 = CH − CH = CH2 — conjugated
CH2 = CH − CH2 − CH2 − CH − CH3 — Isolated
HC = C = CH — Commulatated doublebond
Allene having cumulated double bond
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.

Contact: 8171000425, 7252022576
R/S nomenclature in Allene:-
(1)
Trick- number start from in plane side group.
(2)
(3)
* Spiranes:- Derivative of Allene
Note:-
This type of molecule doe not show axial chirality because terminal carbon not lie in Cz axis

Contact: 8171000425, 7252022576
*Central Chirality in spiranes:- Chiral due or chiral centre
Example-1
Example-2
Example-3
Example-4

Contact: 8171000425, 7252022576
BIPHENYLS:-
Essential conditions for chirality of 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.

Contact: 8171000425, 7252022576
Note:- Butteressing effect
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.
It is due to ocetword bonding of ortho substituent by m-due to steric reason.
Bultersing effect increase with increasing of the size m substituent.
I < II < III (order of activation)
Br > Me > Cl > NO2> COOH > F > H
Bultersing order(m-substituent)
Briged Biphenyls:-
if n = 1 – achiral due to r-plane
if n = 2,3 — chiral

Contact: 8171000425, 7252022576
* Atropisomerism:- A molecule which is chiral due to oispictiction of rotation rivotal bond is

known as atropisomer and this phenomenon is known as atropisomerism.
* Chiral due to chiral plane:-
(1) Ansa-compounds:-
(2) Paracyclophane:-

Contact: 8171000425, 7252022576
(3) Trans-cyclootences:-
(4) Helicity:-
(i) For Helicity compound have minimum six ring
(ii) For helicity if the substituent are present then minimum have 3 in angular fashion.
P(+) → Clockwise
M(-) → Anti cloclwise
Note:- For prediction of P/M i.e. configuration in hedical structure, we strict from above to
below [M].

Contact: 8171000425, 7252022576
* Organometallic compounds
Example-1.
Example-2.
Example-3.

Contact: 8171000425, 7252022576
Types of Stereoisomers:-
(1) Stereochemical Relation:-
(a) Enantiomers (Relative)
(b) Diastoreomers (Relative)
(c) Meso compounds
(a) Enantiomers (Relative):- Those molecules which are non-superimpose mirror image
with each other are known as enantiomer & this property is known enantiomers.
Note:- Enantiomers are always chiral molecules:-
How to identity enantiomers?
(i) On the basis of mirror image:-
(ii) R/S nomerclature.
No of Chiral centre Molecule (A) Molecule (B)

(a) One R S
(b) Two R, R, S, S
Or Or
S, S, R, R,
R, S, S, R S, R, R, S
(c) three R, R, R, S, S, S, S,S,S R,R,R
RSR so on SRS so on
Example:-

Contact: 8171000425, 7252022576
(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.
(2) They rotate parallel to opposite direction bur in equal magnitude.
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.
(5) They have different playsilogical properties, Example:-
(-) nicotin is more possisonueous then (+) nicotin
(+) Histidine more surety

Contact: 8171000425, 7252022576
(-) Histidine tastless
(+) Limonene- orange smell
(-) Limonene – Lemon smell
Enantiomers can’t be distinguished by H-NMR system in achiral medium (solvent) but they
can be distinguished in chiral medium.
* Resolution:- Separation of enantiomers from its recimic mixture is known as resolution.
* 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.
RRR SSR → [D]
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.
Meso compounds are optically inactive due to internal compensation.

Contact: 8171000425, 7252022576
Homomers:- Homomers are identical with each other
Question:-The IUPAC name of the following compound is [NET Dec 2011]
(a) (R)-3-(prop-2-enyl)hex-5-ynoic acid (b) (S)-3-(prop-2-enyl)hex-5-ynoic acid
(c) (R)-3-(prop-2-enyl)hex-5-enoic acid (d) (S)-3-(prop-2-ynyl)hex-5-enoic acid
Solution
(S)-3-(prop-2-enyl)hex-5-ynoic acid

Contact: 8171000425, 7252022576
UMBRELLA INVERSION [NITROGEN INVERSION] OR PYRAMIDAL INVERSION
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)
But N having four different group it will be chiral

Contact: 8171000425, 7252022576
Prochirality and Topicity
* 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.
In pseudochiral centre, higher priority goes to R configuration
TOPICITY:- Stereo chemical relationship between two or more ligand within a molecule is
defined in terms of topicity.

Contact: 8171000425, 7252022576
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.
(i) Homotopic ligand
(ii) Hetrotopic ligand
(iii) Distereotopic ligand
(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.
(2) Hetrotopic ligand
Two ligands are said to be hetrotopic if they are replaced by in turn by new ligands (chiral)
gives two enantiomers
Hetrotopic ligands also called enantotopic ligands.

Contact: 8171000425, 7252022576
(iii)Diastriotopic ligands:- Diastriotopic ligands ate not symmetry element Cn , I, Sn absent.
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.The first person to separate a racemic mixture into individual enantiomers is
(a) J, H van’t Hoff (b) Pasteur
(c) H.E.Fischer (d) F. Wohler [NET Dec 2012]
Solution (b) Pasteur
Question.In the gcompound given below, the realtion between HA, HB, and between Br1, Br2
is:
(a) HA, HB are enantiotropic; and Br1,Br2are diasterotopic
(b) HA, HB are diastereotopic; and Br1, Br2are enantiotropic
(c) HA, HB are diastereotopic; and Br1, Br2are homotopic
(d) HA, HB are enantiotropic; and Br1, Br2are homotopic[NET Dec 2012]
Solution (b) HA, HB are diastereotopic; and Br1, Br2are enantiotropic

Contact: 8171000425, 7252022576
Note:- (i) Homotopic ligands are interchange by Cn axis
(ii) Enantiotopic ligand are interchange by 𝜎-plane i.e. i and Sn symmetry.
(iii) Diastriotopic ligands are not interchange by any symmetry elements (Cn , 𝑖, Sn absent)
Question. The structure of (2S, 3R)-2-amino-3-hydroxy butanoic acid is [JAM 2015]
Solution. (c)
Question. Among the following, the most stable conformation of meso-2,3-dibromobutane is
[JAM 2016]
Solution.(b)
Question.Catalytic hydrogenation of the following compound produces saturated

hydrocarbon(s). The number of stereoisomer(s) formed is/are [JAM 2017]
(a) (b) 2 (c) 3 (d) 4

Contact: 8171000425, 7252022576
Solution. (c)-3

Contact: 8171000425, 7252022576
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.
Symmetry:- Disatereotopic are not interchange by Cn (Cz ), Sn and i

Contact: 8171000425, 7252022576
Nomenclature of prochiral legands and faces
(1) Prochiral ligands :- (Pro-R & Pro-S)
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.
* Nomenclature of phase (Re or Si)
NOTE:- In Re and Si nomenclature, Ist priority always gives oxygen and then according
Re For Top site

[ ]
Si for bottom site

Contact: 8171000425, 7252022576
* 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
(i) number of optical isomer = 2n−1

𝑛−2
(ii) number of meso compounds = 2 2
Total stereoisomer = optical active + meso
(ii) if n = odd (3,5,7…….)

𝑛−1
(Number of meso (optically inactive) =2 2

Contact: 8171000425, 7252022576
Optical behaviour of stereosomers:- The stereoisomers which rotate perpendecular are

known as optical isomers and that phenomenon is known optical isomerism
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.
* OPTICAL ROTATION (𝜶)
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
[𝛼]𝜆𝑇 → specific rotation
temp. = 20°C , λ = 589 nm
l = 1dm → 10 cm
concentration = g/mL or g/cm3
If c = 1gm/cm3 or l = 1dm
𝜶 = [𝜶]𝑻𝝀

Contact: 8171000425, 7252022576
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 .
Unit – degree gm-1mL dm-1
Degree gm-1 cm3 dm-1
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
Optical purity or Enantiomeric excess:-
(i) A solution containing a single enantiomers is said to optically pure or enantiomerically

pure.
(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.
Percentage of d % of l Optical purity (ee)

100% 0% 100% w.r.t d
80% 20% 60% w.r.t d
60% 40% 20% w.r.t d
50% 50% 0 w.r.t d
40% 60% 20% w.r.t d
80% 20% 60% w.r.t d
Contact: 8171000425, 7252022576
100% 100% 100% w.r.t d

Optical purity or enantiomers excess
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?
Solution α mix = 12°
α pure = 32°
12
e.e = 32 × 100%
e.e = + 37.5 (d)
optical purity of d isomer 37.5 %
reci mixture l % = 62.5 %

62.5
l%= 2
= 31.25%
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]
(a) +79º (b) 0 (c) –79º (d) +39.5º
α mix
ee = × 100%
α pure
α mix
50 = × 100%
158
50 ×158
= = +79°
100

Contact: 8171000425, 7252022576
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]
(a) 8.6 (b) 77.2 (c) 94.3 (d) 82.9
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%
Solution[𝛼] = 10° αabs = -0
l = 0.6 dm
Concentration = 0.15 g/mL

α
[α]λT = Cl
−0.45 −5°
[α]Tλ = 0.6 ×0.15 = -5° ee = 10
ee = 0.5 → 50 % with respect to 25% R 25% S
Total (R) = 75%, (S) = 25%(d) answer
Question.The [α]D of a 90% optically pure 2-arylpropanoic acid solution is +135°. On

treatment with a base at RT for one hour, [α]D changed to +120°. The optical purity is
reduced to 40% after 3 hours. If so, the optical purity of the solution after 1 hour, and its
[α]D after 3 hours, respectively, would be [NET Dec 2012]
(a) 80% and 60° (b) 70% and 40°
(c) 80% and 90° (d) 70% and 60°

Contact: 8171000425, 7252022576
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
At 3 hours optical purity is 40% So, specific rotation

150
× 40 = 60° Answer(a) 80% and 60°
100
optical purity %d %l Specific Rotation

100% 100% 0% 150°
90% 95% 5% 135°
80% 90% 10% 120°
40% 70% 30% 60°

Contact: 8171000425, 7252022576
CYCLOHEXANE
QuestionThe optically active stereoisomer of the following compound is:[JAM 2011]
Answer (b)
1,4 position–plane pass, whether it is axial or equatorial
Due to H bond, this configuration is more stable (1,3) position
Cyclohexane exists in different form but chair form is most stable form

Contact: 8171000425, 7252022576
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.
After filing all axial group become equilateral and vice-versa
Question Ring flipping of the compound in the following conformation leads to [GATE-2016]
Solution

Contact: 8171000425, 7252022576
Question:- Bridge-head hydrogen of the conformer of cis-decalin is positioned as [GATE 2004]
(a) a, a (b) e, e (c) a, e (d) pseudo-a, pseudo-e
[a = axial; e = equatorial]
Solution Cis-decaline (2-dot) means (cis)
Answer is (c)

Contact: 8171000425, 7252022576
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)
Solution (a) (II) < (III) < (I)
I – Half chair
II – Twist boat
III- True Boat

Contact: 8171000425, 7252022576
CYCLOHEXANE DERIVATIVE:-
Cis-1,3-cyclo hexane diol

Contact: 8171000425, 7252022576

Contact: 8171000425, 7252022576

Contact: 8171000425, 7252022576
Question. The configuration at the two srerocentres in the compound given below are
(a) 1R, 4R (b) 1R, 4S (c) 1S, 4R (d) 1S, 4S
Solution.
Answer is option (a)
QuestionThe absolute configuration at the two chiral centres of (–)–camphore is:
(a) 1R, 4R (b) 1R, 4S (c) 1S, 4R (d) 1S, 4S
Solution
Answer:- (d) 1S, 4S

Contact: 8171000425, 7252022576
* ANOMERIC EFFECT:-
(i) Presence of the pyranose ring.
(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.

Contact: 8171000425, 7252022576
* DIMETHOXY METHANE
Most stable form Gauche form
Question:- Which is most stable?
Question:- Which compound form lactones?
(e) → carbon-elevated carbon
(d) → Carbon- depressed carbon

Contact: 8171000425, 7252022576

Contact: 8171000425, 7252022576
(1) Rate of decarboxylation:-

Contact: 8171000425, 7252022576
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.
Conformer cannot be isolated, because they exist in dynamic equilibrium.
* 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.
* If energy barrier for rotation of single bond is very large than

one conformer cannot be converted into another such conformer
are isolated and also called configuration isomer.

Contact: 8171000425, 7252022576
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.
* Contribution of each torsional strain in potential energy conformer:-
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
* Butane Gauche interaction:- Found in staggered conformer between bulkyer groups/ligands

separated by approximately 60°
* Contribution of each Gauche interaction in potential energy of a conformer 1,3-diaxial

interaction in cyclic compounds:-
X Y
H H 0.00
Me H 0.00
Me Me 0.9 Kcol/mol
Et Et ≤ 0.9 ≈(1) Kcal/mol
Contact: 8171000425, 7252022576
* 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
CH3 − CH2 − CH2 − CH3 n-butane
*NEW MANN PROJECTION FORMULA:-
Potential Energy Diagram for this stability I > III > II > IV

Contact: 8171000425, 7252022576
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
∆G = G2 − G1 free energy (2)
∆G = 3.6 – 1.8 1.8 𝑘𝑐𝑎𝑙/𝑚𝑜𝑙
Question.The gauche conformation (φ = 60°) of n - butane possesses [NET June 2013]
(a) plane of symmetry; and is achiral (b) C2-axis of symmetry: and is chiral

Contact: 8171000425, 7252022576
(c) centre of symmetry; and is achiral (d) plane of symmetry; and is chiral
Solution.
(b) C2-axis of symmetry: and is chiral
(Gauche form is optical active)
* IN LIQUID PHASE:- (Benzene-solvent)
* IN GASEOUS PHASE
In gaseous phase less stable- due to dipole-dipole interaction
* ∝ −halo ketone effect:-

Contact: 8171000425, 7252022576
* (Interaction → repulsion)
* BREDT’S RULE:- (Bridge head carbon does not have planarity)
Rule- Bridge head carbon cannot be sp2 hybridized unless ring size is large enough.
Carbocation/double Bond → not doing exist.
Cause:- Bridgehead and adjacent carbon both are orthogonal to each other that’s why proper
overlapping not tales place.

Contact: 8171000425, 7252022576
Example
Application:-
(i) Stability of 𝐂
(ii) Size of ring

Contact: 8171000425, 7252022576
Stability of B. H. C depends upon ring size (number of atom in a system)
c>b>a
Stability increase
Anti-Bredts Rule:-
Number of bridging carbon = 8
If briding carbon ≥ 8, the compound will be stable

Contact: 8171000425, 7252022576
Cram’s Rule
* Diastereoselectivity in addition reaction of chiral carbonyl compounds
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:-
(1) Cram’s rule

Contact: 8171000425, 7252022576
(2) Dipole cram’s Rule
(3) Fekin-Anti model
(4) Rigid cyclic (Chelation model)
(1) Cram’s Rule:-
(i) Draw the Newmann projection of chiral carbonyl compounds placing bulkiest (large) anti to
carbonyl group
(ii) Allow to nucleophile to attack from side of small group
(iii) Re-draw product in zig-zig fashion
B.D angle → Burgle Dainty angle
Trick
If large group Anti (Nu attack from smaller group side)
If large group syn (Nu attack from medium group side)

Contact: 8171000425, 7252022576
DEMERIT’S OF CRAM’S RULE:-
(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.
Na+ non − chelating ∗ /Li+ often ( when O is hetro atom)

K+
𝐌𝐠 𝟐+
Contact: 8171000425, 7252022576
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.
* TRICK → [For chelating]
(*) 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.

Contact: 8171000425, 7252022576

Contact: 8171000425, 7252022576

Contact: 8171000425, 7252022576
Geometrical Isomerism:- It is also called cis-trans isomerism.
(1) Geometrical isomerism are alway diastereomers
(2) Geometrical isomerism are also a type of stereoismerism
(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.
Structural isomerism can be divided into following categories.

Contact: 8171000425, 7252022576
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.
iso-one Me group at second last or second first in chain
𝐂𝟓 𝐇𝟏𝟐
𝐂𝟒 𝐇𝟏𝟎 𝐎
𝐂𝟒 𝐇 𝟖

Contact: 8171000425, 7252022576
Position isomerism:-
Compounds which have same Molecular formula but different in the position of functional
groups.

Contact: 8171000425, 7252022576
FUNCTION GROUP ISOMERISM
Compound having same molecular formula but different 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)

Stereo Chemistry Notes

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Stereo Chemistry Notes

Uploaded by

Copyright:

Available Formats

44-Karanpur, Near Luxmi Narayan Mandir, Dehradun

Contact: 8171000425, 7252022576

Institute for CSIR-UGC-NET/JRF, GATE & IIT-JAM

(1) σv – vertical plane– plane parallel to principle axis.

(2) σh – Horizontal plane or molecular plane.

(3) σd – Dihydral plane (operation reflexion).

σh – plane perpendicular to principle axis.

σd – place bisect two Cz angle.

(3) Inversion centre (centre of symmetry):- (i) operation–inversion

Note:- i present → optically inactive compound

(4) Improper axis of symmetry (Sn):- (Operation – Roto-reflexion)

Rotation followed by reflexion in a plane perpendicular to the axis generate a structure

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 1

(5) Indentity (𝜺) – (operation-nothing to do)

* CIP Rules:- (Cahn-Inglod-Prelog):-

Assign priority of the different substituents accordingly.

(i) Lowest priority group must away from observer.

(ii) Rotates the eye with decreasing order of priority.

Note:- RS nomenclature always gives chiral molecule

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 2

Fisher representation:- (2-D) [R]

* Mesotartic acid is optically inactive due to internal compensation

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 3

(5) Note:- Fisher representation always show eclipsed form.

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 4

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 5

* Saw-horse projection formula

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 6

Serine is the standard of amine which is—

→ All amino acids having S configuration except cystein

→ Generally relative configuration used in carbohydrates and amino acids

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 7

(i) Axial chirality:- Axial chirality show following compounds— [ABS]

(iii) Spyraives (spiranes)

CH2 = CH − CH = CH2 — conjugated

CH2 = CH − CH2 − CH2 − CH − CH3 — Isolated

Allene having cumulated double bond

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 8

R/S nomenclature in Allene:-

Trick- number start from in plane side group.

* Spiranes:- Derivative of Allene

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 9

*Central Chirality in spiranes:- Chiral due or chiral centre

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 10

Essential conditions for chirality of biphenyls:-

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 11

Note:- Butteressing effect

It is due to ocetword bonding of ortho substituent by m-due to steric reason.

Bultersing effect increase with increasing of the size m substituent.

I < II < III (order of activation)

Br > Me > Cl > NO2> COOH > F > H

if n = 1 – achiral due to r-plane

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 12

* Atropisomerism:- A molecule which is chiral due to oispictiction of rotation rivotal bond is

* Chiral due to chiral plane:-

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 13

(i) For Helicity compound have minimum six ring

M(-) → Anti cloclwise

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 14

Institute for CSIR-UGC-NET/JRF, GATE, IIT-JAM, B.Sc. & M.Sc Page | 15

(1) Stereochemical Relation:-

(a) Enantiomers (Relative)

(b) Diastoreomers (Relative)