MADHAPUR

REDUCTION

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 REDUCTION

Reduction

Catalytic reduction Chemical reduction

Reduction by Hydride transfer catalysis

dissolving metals

Catalytic reduction

H 2 gas is passed over metal catalysts like Pt, Pd, Raney Ni /  (Raney Ni is
finely divided Ni saturated with hydrogen. It is obtained by the reaction of
Ni-Al alloy with NaOH solution.)

Catalytic reduction is the most convenient method of reduction. However, it is

not preferred since it is non-selective in nature i.e. it reduces carbonyl group,
COOH along with any double bond or triple bond.

Homogenous hydrogenation

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Egs Wilkinson catalyst -(PPh3)3RhCl, (PPh3)3RuCl H

Heterogenous catalysis is non-selective, it depends more on chemisorption and not

on reaction between the molecules. These difficulties are overcome by the
introduction of soluble catalysts which allow hydrogenation in homogenous
solution.

The Wilkinson catalyst is an extremely efficient catalyst for hydrogenation of non-

conjugated alkenes and alkynes at ordinary temperatures and pressure in benzene
or similar solvents.

Functional groups such as oxo, cyano, nitro, chloro, azo are not reduced under the
given condition. Mono- and disubstituted double bonds are reduced much more
rapidly than tri- or tetra substituted ones, permitting g the partial hydrogenation
of compounds containing different kinds of double bonds.

OH OH

2)

H , ( C H ) P  RhCl
3) C6 H5CH = CHNO2 ⎯⎯⎯⎯⎯⎯
2  2 5 3 3
C6H6
⎯
→ C6 H5CH 2CH 2 NO2
An important practical advantage is in addition to selectivity only two deuterium
atoms can be added (partial hydrogenation)

4)

CHEMICAL REDUCTION

Reduction by dissolving metals

1. Metal is source of electron and proton donor may be water, alcohol or an

acid

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2. common metals used are alkali metals, Ca, Zn, Mg, Sn and Fe

3. Alkali metals are often used in liquid ammonia solution

ex: Birch reduction Na in liquid ammonia; Clemenson’s reduction- Zn-Hg

/HCl; Bouveaults-Blanc reaction- Na in alcohol.

Hydride transfer catalysis

Ex: -LiH, LiAlH4, DIBAL,NaBH4 andNaBH3CN (In these cases products obtained
should be subjected to acidic hydrolysis to get the final reduced product)

NaBH3CN is a weaker and more selective than sodium boro hydride.it is stable
H
in acidic condition ( P =3) and can be employed for reduction in the
presence of functional groups which are sensitive to the more basic condition
of reduction with sodium boro hydride

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 LiAlH4

BASE NUCLEOPHILE

LiAlH4 Nucleophilic addn SN2

x Alkyl halides
epoxides, ROTS.

1,2 addn. (Substrate has polarised multiple bond) 1,4 addn (conjugate
system like cinnamyl
SUBSTRATE PRODUCT system)
H
RCHO, RCOOH RCH2OH C C C H
H
RCOR RCH2OH O

RCOCl
RCH(OH)R
O OH LiAlH4 30°C ether
R H C R H2CR C R
C H H H2 H2
RCOOR' RCH2OH + R'OH C C CH2OH

RCONR2 RCH2NR2
RCOOH RCH2OH
R C N RCH2NH2
RNO2 RNH2
ArNO2 ArN=N-Ar

+
Note : Epoxide coordinates with AlCl3 to give C transition state

NaBH4 is relatively less strong a reducing agent then LiAlH4 . NaBH4 doesn’t react
with H2O . Hence for the reduction of polyhydroxy compounds like carbohydrates in
aqueous. medium it is preferred.

GLUCOSE(aq) ⎯⎯⎯
SBH
→ SORBITOL

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Reducing agent. ALKENE ALDEHYDE KETONE ESTER AMIDE COOH
H2 /Pt/Pd/Ni/  Alkane 1° Alc. 2° alc 1° alc. Amine 1 °
alc
LiAlH4 - 1° alc 2° alc 1° alc Amine 1° alc
NaBH4 - 1° alc 2° alc - - -
DIBAL - 1° alc 2° alc. Aldehyde Aldehyde 1°
CH3 CH3 alc.

N CH3
H

The best reducing agent for reduction of carboxylic acids is Borane since Hydride
transfer catalyst being alkaline in nature reacts with acid leading to wastage of
catalyst.

Sterically hindered reducing agents like DIBAL can be used to reduce esters to
aldehydes by using one equivalent of DIBAL at low temperature.

DIBAL is preferred for reduction of ester and amide to aldehyde, cyano gp to imine
gp (CH=NH)

Alcohols can be reduced to alkane by the use of red P and HI.

Alane reduces carbonyl gp, epoxides, esters, acyl halides and acid anhydrides to
alcohols.

It also reduces CN, - N-OH, imine and amide to amine.

Borane reduces −CHO and −COOH group TO 1° alcohol

Reducible gp Reduced to
−CH = CH2
CH 2 C B

−C  N −CH2NH2
R R
C N CH 2 N

O R R

2 ROH
O

R
O
R

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 OH
Ni/H2
CH 2OH
O O
CH 2NH 2
C OR OH
LiAlH4
CH 2OH
C N H3 O+
CH 2NH 2
OH
NABH4
COOR
H3 O+
CN
OH
DiBAL CHO
+
H3 O
CHO

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