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CHM 624

Zurhana Bt Mat Hussin


Chemistry Lecturer
Tel: 019-9965343

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.

2. Describe, illustrate, and propose the processes involved


towards the synthesis of complex molecules.

3.Critically review, intergrate and consolidate knowledge


and skills and practices in organic chemistry
4. Observe, plan, conduct and justify scientific
investigation in organic reactions and syntheses.

5. Interpret, use and evaluate a wide range of data to


solve problems of both familiar and unfamiliar nature.

6. Communicate and collaborate with groups of peers to


discuss chemical problems and identifying solutions in
both the labs and classroom.
Topics covered
O Selectivity in Organic Chemistry
O Chemoselectivity
O Regioselectivity
O Stereoselectivity
O Oxidation
O Metal and non-metal based reagents
O Epoxidation
O Reduction
O Hydrogenation
O Boron reagents
O Aluminium reagents
Topics covered (cont.)
O Protecting Groups
O Hydroxyl compounds
O Ketones and aldehydes
O Amines
O Carbon-carbon bond formation
O C-C and C=C bond formations
O Alkylation of enolates, enamines and hydrazones
O Claisen rearrangement
O Wittig reaction
O Peterson olefination
O Total Synthesis of Natural product
CHAPTER 1

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

cold conc. HCl

halogenation of tert alcohol


Reactions involving discrimination between
different sites in the same substrate

O Can be described as product selectivity and


involves a reaction in which more than one product
can be formed but in which the products are
formed in a ratio which differs from the expected
one

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

fumarase (an enzyme)


Definitions of selectivity
O Chemoselectivity
O Discrimination shown by a reagent in its reaction with
different functional groups, i.e. Its preferential reaction with
one functional group in a molecule containing two (or
more) functional groups
O 1. Reduction :

NaBH4

H2/ Pd-C
2. Epoxidation
O Regioselectivity

O Preferential reaction at one (or more) possible sites in


a molecule resulting in the preferential formation of
one (or more) structural isomers.

O 1. Friedel Crafts reaction

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.

O Simple diastereoselectivity can occur in any


reaction in which two or more new stereogenic
centres are created even when the reaction
involves an achiral substrate and achiral
reagent.
chiral centre

H2

Nickel

racemic

chiral centre
O Absolute diastereoselectivity

O Is seen in the reaction of a chiral substrate with


an achiral reagent

1. BH3/THF

2. H2O2, - OH

Anti-Markovnikov
Stereotopic and stereofacial selectivity
O Facial selectivity

O Situation where one of the faces of the


molecule is preferentially attacked by a
reagent. Thus, new stereogenic centres can
also be created by discrimination between two
apparently identical atoms or groups.

O Terms such as homotopic, enantiotopic and


diastereotopic are used to describe the
stereochemical relationship between groups or
faces in the molecule
O Homotopic

O Groups are homotopic if they can be interchanged by


rotation about an axis of symmetry

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.

O Transformation of enantiopic groups or addition to


enantiopic faces, usuallly give rise to enantiomers

1 equiv. MeCOOH

H+
esterification

PhCOOOH

epoxidation
O Diastereotopic

O Two groups which cannot be interchanged by any


symmetry operations are described as diastereoisotopic.
Similarly, the two faces are diastereoisotopic if the plane
dividing them is not plane of symmetry and does not
contain an axis of symmetry. Transformations of
diastereotopic groups or addition to diastereotopic faces
give rise to diastereoisomers

NaBH4
EXERCISE

1. Briefly explain what is meant by the following terms:


i) Diastereoselectivity
ii) Enantiomers
iii) Homotopic
iv) Regioselectivity
v) Racemic mixture

2. What is the difference between enantioselectivity and


diastereoselectivity ? Explain your answer with examples ?
3.
4.
5.

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