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Email: zurhana_mhussin@pahang.uitm.edu.my
OBJECTIVES
1. State, write and explain the concepts of selectivity in
organic chemistry, oxidation and reduction, protective
groups in organic chemistry, and carbon-carbon bond
formation.
SELECTIVITY IN ORGANIC
CHEMISTRY
What is selectivity?
O Organic chemistry particularly organic
synthesis depends upon selectivity which can
be achieved in any organic reactions
O Selectivity discrimination observed in a
reaction involving competitive attack on two or
more substrates or at two or more positions,
groups or faces in the same substrate
O Several kinds of selectivity can be identified
and as a result different level of control can be
exercised over the outcome of the organic
reactions
Reactions involving discrimination
between different substrates
O Described as substrate selectivity and involves a
reagent which transforms different substrates, say
A and B, under same conditions at different rates,
into the products C and D
1 mole H 2
catalyst
only one hydrogenate
isomers
H2SO4
SO3 35C
32% 6% 62%
O Discrimination between different groups or faces can lead to
the preferential formation of one (or more) diastereoisomers
and this type of selectivity is defined as diastereoselectivity
1. BH3/THF
2. H2O2, -OH
1. EtMgBr
2. H3O+
3 : 1
O In some situation discrimination between different
groups or faces leads to the preferential formation
of one enantiomer and this is known as
enantioselectivity
H2O
NaBH4
H2/ Pd-C
2. Epoxidation
O Regioselectivity
H2SO4
SO3 35C
32% 6% 62%
2. Hydration
3. Diels Alder Reaction
O Stereoselectivity
O Preferential formation of one (or more) products that differ
only in their configuration. Stereoselectivity can be further
divided into enantioselectivity and diastereoselectivity.
O Enantioselectivity
O Occurs when the two stereoisomeric products which can
be formed are enantiomers.
chiral reagent
enantiomers
Chiral reducing
agent
O Diastereoselectivity
O Occurs when the products which can be formed
are diastereoisomers. Diastereoselectivity can
further be divided into two types simple and
absolute diastereoselectivity.
H2
Nickel
racemic
chiral centre
O Absolute diastereoselectivity
1. BH3/THF
2. H2O2, - OH
Anti-Markovnikov
Stereotopic and stereofacial selectivity
O Facial selectivity
Br2
NaBH4
O Enantiotopic
O Two groups are enantiotopic if they are related to one
another by a plane or centre of symmetry. Similarly, two
faces are enantiotopic if the plane dividing them is a plane
of symmetry which does not contain a coplanar axis of
symmetry.
1 equiv. MeCOOH
H+
esterification
PhCOOOH
epoxidation
O Diastereotopic
NaBH4
EXERCISE