Lecture-6

Classical and Non-classical Carbocations

• Non-classical carbocation: A non-classical carbocation is an ion containing a
positively charged carbon atom having a three-centre two-electron structure. This
means there are three atoms sharing two electrons. This type of electron sharing is
called as delocalization of the electrons.
• These type of carbocations are not stabilized by resonance
• But, neighbouring group participation (NGP) can stabilize the carbocation
• Stabilizes the delocalization of sigma electrons of C-C or C-H or pi-electrons of C=C

Neighbouring group participation: Also known as Anchimeric Assistance

• It is an interaction of a reaction center with a lone pair of electrons in an atom or the
electrons present in a pi bond contained within the parent molecule but not
conjugated with the reaction center.
• When NGP is in operation reaction rate will be increased.
• Possible for the stereochemistry of the reaction to be abnormal (or unexpected)
when compared with a normal reaction.
 Classical and Non-classical Carbocations
1. NGP by heteroatom lone pairs:

2. NGP by an alkene:
• The π orbitals of an alkene can stabilize a transition state by helping to delocalize the
positive charge of the carbocation.

Unsaturated tosylate will react more quickly (1011 times faster

for aqueous solvolysis) with a nucleophile than saturated
tosylate.
 Classical and Non-classical Carbocations

Delocalization of C-C double bond stabilizes the carbocation (non-classical)

Even if the alkene is more remote from the reacting center the alkene can still able
to delocalize the carbocation.
 Classical and Non-classical Carbocations
3. NGP by a cyclopropane, cyclobutane or a homoallyl group:
• If Cyclopropylmethyl chloride is reacted with ethanol and water then a mixture of
48% cyclopropyl methyl alcohol, 47% cyclobutanol and 5% homoallyl alcohol (but-3-enol) is
obtained. This is because the carbocationic intermediate is delocalised onto many different
carbons through a reversible ring opening.
 Classical and Non-classical Carbocations

4. NGP by an aromatic ring: An aromatic ring can assist in the formation of a

carbocationic intermediate called a phenonium ion by delocalizing the positive charge.
Classical and Non-classical Carbocations
Classical and Non-classical Carbocations
 R3C + LA–X LA: Ag , AlCl3, Generation
Carbocation SnCl4, SbCl5, SbF5, BF3, FeCl3, ZnCl2, PCl3, PCl5,
rbocation Generation X: F, Cl, Br, I, OR
Removal of an energy-poor anion from a neutral precursor via Lewis Acids
• Removal of an energy-poor anion from a neutral precursor via Lewis Acids
Lewis Acids
Acidic dehydratization of secondary and tertiary alcohols
R3C X + LA R3C + LA–X LA: Ag , AlCl3, SnCl4,
nd tertiary alcohols
LA: Ag - H2O , BF R: Aryl + other ch
R3C, AlCl
OH3, +SnCl 4, SbCl5, SbF
H–X 5 R3 , FeCl3,+ZnCl
3C X2, PCl3, PCl5, POCl3 ...
X: F, Cl, Br, I, OR X: SO42-, ClO4-, F
R: Aryl + other charge stabilizing substituents
R3C + X
X: SO42-
Acidic dehydratization of secondary , ClO
and
-
4 , FSO
tertiary
-
3 , CF3SO3
alcohols
-

• From
Fromneutral
neutralprecursors
precursors viavia heterolytic
heterolyticdissociation
dissociation (solvolysis)
(solvolysis) – First
- First step step
in SNin SN
1 or
1
E1 re
or E1 reaction - H2O R: Aryl + other charge
R3C OH + H–X R 3C + X
c dissociation (solvolysis) - Firstsolvent
step in SN1 or E1 reactions X: SO42-, ClO4-, FSO3-
R3C X R3C + X Ability of X to function as a leaving g
R: Aryl + other charge stabilizing substituents -N2+ > -OSO2R' > -OPO(OR')2 > -I •
C + X X: SO42- , ClO4of-, X
Ability FSO -
3 , CF3SO
to function as3-a leaving group:
From neutral precursors via heterolytic dissociation (solvolysis) - First step in SN1 or E1 reactio
-N2+ > -OSO2R' > -OPO(OR')2 > -I • -Br > Cl > OH2+ ...
Addition of electrophiles to š-systems
solvent
s) - First step in SN1 orRE1
3C reactions
X R3C + X Ability of X to function as a leaving group:
-N + > -OSO R' > -OPO(OR') > -I • -Br >
 LA–X - H2O R: Aryl + other cha
R3C OH + H–X X:R3F, Cl, Br,+I, OR
CGeneration X
Carbocation X: SO42-, ClO4-, FS
Acidic dehydratization of secondary and tertiary alcohols
• Acidic dehydration of secondary / tertiary alcohols
ols From neutral precursors via heterolytic
- H O
dissociation (solvolysis) - First step in R:
SN1Aryl
or E1
+ rea
othe
R3C OH + H–X 2 R3C + X
X: SO42-, ClO4
solvent
R: RAryl
3C +Xother charge stabilizing
R3C substituents
+ X Ability of X to function as a leaving gr
X: SO42-, ClO4-, FSO3-, CF3SO3- -N2+ > -OSO2R' > -OPO(OR')2 > -I • -
From neutral precursors via heterolytic dissociation (solvolysis) - First step in SN1 or E1

Addition
lvolysis) of electrophiles
- First step SN1 or E1to š-systems
• Addition of in
electrophilereactions
solvent
/ proton to an alkene
R3C X R3C + X Ability of X to function as a leavin
R R R R
-N2+ > -OSO2R' > -OPO(OR')2 >
H R
Ability of X to function as a leaving Hgroup: R R
+ H + ... R
-N2 > -OSO2R' > -OPO(OR')
R R 2 > -I • -Br > Cl > R
OH2 R H
Addition of electrophiles to š-systems

Hydride abstraction from neutral precursors

R R H R R H R
 Carbocations at the bridge head systems

Bridgehead Carbocations Me
Me OTs wh
Me rea
TsO TsO TsO

The relative rate of acetolysis: 1 10-7 10-13 104

Bridgehead carbocations are highly disfavored due to a strain increas
achieving planarity. Systems with the greatest strain increase upon p
from ground state to transition state react slowest.
Q. Out of the given two, which one is less stable carbocations?

• It is impossible to form carbocation at bridgehead atoms. Since they can not be

planar. However, larger bridgehead carbocations can exist (ring size 8 or more).
• Ring size lesser than 8 have ring strain as well as angle strain.
• Bridge head carbocations are unstable because according to Bredt’s rule the
bridge head carbons cannot form double bonds (never have sp2 or sp hybridized
because of the high rigidity). This is because they are out of plane which results in
a drastic angle strain between the atoms.
Note: Bredt’s rule is only applicable for rings having less than 8 members.
Explain the observations?
Explain the observations?
Semipinacol rearrangement
 either an alkyl substituent or a hydride is involved, the term Wagner-Meerwein shift is
employed to identify this class of rearrangments.
Carbocations: [1,2]-sigmatropic rearrangements
❖ 1,2-Sigmatropic shifts are the most commonly encountered cationic rearrangements
when either an Alkyl substituent or a hydride is involved.
Stereoelectronic requirement for migration....

retention of stereochemistry

C C
A D A D
B bridging T.S. B

C
A D
B