Carbanion Rearrangements:

Carban ion
Rearrangements
Aldol condensation

Favorskii rearrangement

Wittig Rearrangement
Aldehydes and ketones having at least one α-hydrogen can undergo
Aldol condensation reaction.
In the presence of dilute alkali as catalyst, aldehydes and ketones form
α-hydroxy aldehydes (aldol) or α-hydroxyketones (ketol) as product.
When aldol condensation is carried out using same aldehyde or ketone,
it is called Self-aldol condensation.
Pharmaceutical Applications
Asymmetric aldol reactions play a crucial role
in the drive to create synthetic versions of
biologically active natural compounds.
Chemists are using the reactions - which
create carbon-carbon bonds with tight
stereochemical control - to synthesize
complex biomolecules, many of which have
potential as new drugs, and to reach a deeper
understanding of biosynthetic pathways.    
The aldol reaction fits in easily with
nature’s chemistry. As John Cornforth,
winner of the Nobel prize for chemistry
in 1975 for his work on asymmetry and
enzyme action, said: ’Nature, it seems,
is an organic chemist having some
predilection for the aldol and related
condensations.’ 
Natural Aspect of Aldols
Aldolases are a group of enzymes used in nature to
form carbon-carbon bonds. Several of these are
now commercially available on a scale large enough
for preparative chemistry and they are being
applied increasingly as chiral catalysts for in vitro
synthesis of asymmetric compounds. They have the
advantage of reacting under mild conditions, which
often allows a synthesis to be simplified by
eliminating the need for protection and
deprotection of functional groups.  
Antibodies, many of which are aldolase antibodies,
are also being used as biocatalysts in aldol
reactions. Immunising animals with substrates such
as diketones has generated a number of catalytic
antibodies whose substrate specificities differ from
those of enzymes, thereby extending the potential
range of aldol reactions. These antibodies have
been used in pro-drug activation studies in cancer
therapy and to synthesise complex natural products
such as the pesticides frontalin and brevicomin. 
The aldol reaction is especially relevant to
natural product chemistry, where the new
reagents and techniques can determine the
stereochemistry around individual atoms in a
complex molecule.    
Asymmetric aldol reactions are also being used to
synthesise and study potential new anticancer
agents. ’The most important natural product
application of the aldol reaction today is probably
to the polyketides found in marine organisms, such
as sponges,’ says Mahrwald. 
The synthesis of complex sponge molecules such as
dictyostatin, which has a similar mechanism of
action to Taxol, a widely used cancer therapy.