METAL BASED
REDUCTION
TOPICS
Birch reduction
Pinacol formation
Acyloin formation
1.BIRCH REDUCTION
When aromatic rings are reduced with alkali metal in liquid ammonia or amine in
the presence of alcohol, addition of hydrogen takes place at posilions-1 and -4 to
give an unconjugated diene. This is known as Birch reduction.
This reaction greatly increased the utility of benzenoid compounds in
cyclic synthesis .
Reaction
Mechanism
Lithium, Sodium, Potassium can be used as metals.
Liquid ammonia serves as solvent. Primary amines may also be used as solvent .
I. The metal transfers one electron to the benzene ring to produce a resonance-stabilized anion radical .
II. The radicle accepts a proton from the alcohol to form a radical .
III. The addition of an electron from the metal to the radical produces an anion
IV. The anion which subsequently takes up a proton from the alcohol to give the dihydro product.
Scope and limitation
The presence of EWG like COOH or CONH2in the aromatic rings makes the rings more electron-
accepting and hence the reaction is facilitated. The presence of EDG LIKE Alkyl or Alkoxy have,
the reverse effect . With substituted benzene the electron-donating group remains on the
unsaturated carbon and the electron-withdrawing group remain on the saturated carbon in the
products. When EDG are used, the protonation tends to occur at the ortho or meta positions (with
respect to the substituent).When EWG are used, the protonation generally occurs at the para
position.
Halogens ,aldehydes ketones and nitro groups are reduced in the preference to the
aromatic ring .
Formation of 1,4 diene is more favorable than 1,3 diene this is on the basis of
principles of least motion
examples
2.PINACOL FORMATION
The pinacol coupling reaction, a reductive coupling reaction of carbonyl compounds that
proceeds through the formation of ketyl radical intermediates, affords the corresponding
1,2-diols in one step.
This reaction involves the reductive homo-coupling of a carbonyl compound to produce a
symmetrically substituted 1,2-diol.
Reduction of ketones with dissolving metals in absence of proton donor leads
Reaction
2
Mechanism
The first step in the reaction mechanism is a one-electron reduction of the carbonyl group by
a reducing agent —such as magnesium— to a ketyl radical anion species.
Two ketyl groups react in a coupling reaction yielding a vicinal diol with both hydroxyl
groups deprotonated.
Addition of water or another proton donor gives the diol
The reaction is named after pinacol (2,3-dimethyl-2,3-butanediol ) which is the product
of the reaction when done with acetone
3.ACYLOIN FORMATION REACTION
The bimolecular reductive coupling of carboxylic esters by reaction with metallic
sodium in an inert solvent under reflux gives an α-hydroxyketone, which is known as
an acyloin.
This reaction is favoured when R is an alkyl. With longer alkyl chains, higher boiling
solvents can be used.
REACTION
ACYLOIN
MECHANISM
The mechanism consists of four steps:
(1) Oxidative ionization of two sodium atoms
on the double bond of two ester
molecules
.
(2) Free radical coupling between two
molecules of the homolytic ester
derivative. Alkoxy-eliminations in both
sides occur, producing a 1,2-diketone.
(3) Oxidative ionization of two sodium atoms
on both diketone double bonds. The
sodium enodiolate is formed.
(4) Neutralization with water to form the
enodiol, which tautomerizes to acyloin.
The intramolecular version of this reaction has been used extensively to close rings of different sizes, e.g.
paracyclophanes or catenanes.
If the reaction is carried out in the presence of a proton donor, such as alcohol, simple reduction of the
ester to the alcohol takes place (Bouveault-Blanc Reduction).
APPLICATIONS
.Acyloin Condensation is use in the Preparation of cyclic acyloins . Long-chain dicarboxylic esters have
been converted to large-ring compounds without high dilution technique. The method is the best for
closing rings of ten members or more.
2.Preparation of catenane an interesting and unique compound called catenane, a compound with
interlocking rings, was formed when acyloin condensation was employed for ring closure with ester of
34-carbon dicarboxylic acid.
Thank you
ANNA MARIYA PETER
