Forman Christian College

A chartered University

Furqan Alee
14-10239
shazi5250@yahoo.com
Bond Cleavage
Heterolytic Cleavage

A : B → A + : B − A : B A– : B+

+vely charged ion – carbocation

-vely charged ion – carbaanion

• Reactant intermediate product

 A very important way of generating carbon
nucleophiles involves removal of a proton from a
carbon by a base. The anions produced are
carbanions.
The negative charge gives good nucleophilic
properties and it can be used in the formation of new
carbon carbon bond.
 Carbanion
• Pyramidal - sp3 hybridised
bond angle 109.28.geometery is thus tetrahedral

• Has eight electrons

• Stabilized by resonance or by inductive effect.

.. sp3 hybrid orbital

containing lone pair

Tetrahedral structure of carboanion

•The efficient generation of a significant equilibrium concentration of
a carbanion requires choice of a proper base.

•The equilibrium will favor carbanion formation only when the

acidity of the carbon acid is greater than that of the conjugate acid
corresponding to the base used for deprotonation.

O O-
+ OH- + H2O
R CH3 R CH2
rong base, but it is sufficiently bulky so as to be relatively nonnucleophil

1 mean more product.

1 mean more reactent.
 Stability of Carbanion
depends upon three factors:
(i) By resonance
-
-
H
H
H

Cyclopentadienyl carbanion
 Stability of Carbanion
(ii) By inductive

CH3 CH3 CH3

CH3 C CH3 C H C

CH3 H H

3° 2° 1°
 Stability of Carbanion
(iii) Electron-donating groups destabilize
a carbanion while electron-withdrawing
groups stabilize it.
− −
CH 2 CH 2

>
NO 2 O C H 3
• An ordering of some important substituents
with respect to their ability to stabilize
carbanion can be established.
NO2> COR>CN-CO2R>SOR>Ph-SR>H>R
• F stabilizes CH2X−
more effectively than
Cl, Br, and I because
of the fluorine
electronegativity.
Consider the elimination of 2-fluoropentane …
A carbanion-like transition state
Same typical examples of proton abstraction
equilibria
O O
-
R + NH2 R + NH3
R' R'
(-)

O O
R + NR''2- R + HNR''2
OR' OR'
(-)

O O O O
-
+ R'O + R'OH
R'O OR' R'O OR'
(-)

O O O O
-
+ R'O + R'OH
OR' R'O OR'
(-)

O O
N C + R'O- N C + R'OH
OR' OR'
(-)

R NO2
R NO2 + OH- + H2O
(-)
 Electron delocalization in the corresponding
carbanions
O O- O O-
R R ; R R
R' R' OR' OR'
(-) (-)

O O O O- O- O
R'O OR' R'O OR' R'O OR'
(-)

O O O O
-
O
-
O
OR' OR' OR'
(-)

O O
- O
N C N C N C C
OR' OR'
(-) OR'

O O-
R N+ R N+
O- O
-
(-)
carbon nucleophiles.
 Organometallic Compounds
An organic compound containing a carbon–metal bond

Organolithium compounds and organomagnesium

compounds are two of the most common organometallic
compounds

18
19
 Coupling Reactions

Example of carbon–carbon formation using the

Gilman reaction:

20
Alkylation of Alkynes:
Anions of Terminal Alkynes
CYANIDE ANIONS:
 The witting reaction :

Wittig reported a method for the synthesis of alkenes from

aldehydesand ketones using compounds called phosphonium
ylides.
m
 Enolates
The anions formed by deprotonation of the carbon
alpha to a carbonyl group bear most of their
negative charge on oxygen and are referred to as
enolates
 enolate anion: Enolate are important intermediate
because they react at carbon to create new carbon-carbon
bonds in two types of reactions.

First, they can function

as nucleophiles
substitution reactions.

• Second, they function as

nucleophiles addition. in
carbonyl addition
reactions
Why Carbon of enolate ion
attack?
 Kinetic vs. Thermodynamic Enolates

Kinetic control
Experimental conditions under
which the composition of the
product mixture is determined by
the relative rates of formation of
each product.
Thermodynamic control
Experimental conditions that
permit the establishment of
equilibrium between two or more
products of a reaction. The
composition of the product
mixture is determined by the
relative stabilities of the products.
Kinetic vs. Thermodynamic
Enolates
a) Aldol condensation. The reaction of an aldehyde or ketone
with dilute base or acid to form a beta-hydroxycarbonyl product.

OH
dil. NaOH
CH3CH=O CH3CHCH2CH O
acetaldehyde 3-hydroxybutanal

O OH O
dil. NaOH
CH3CCH3 CH3CCH2CCH3
acetone CH3
4-hydroxy-4-methyl-2-pentanone
 O O OH
dil. NaOH CH3
C C C
H3C CH3 H3C C CH3
H2

OH + H2O

O O O O
CH3
C C C C
H3C CH2 H3C CH3 H3C C CH3
H2

+ H2O