CAM

Lecture 9a
Isomerism Part 1
 Isomers
Molecules with the same molecular
formulae but with different arrangements
of atoms

Stereoisomers
Structural isomers

Chain isomers Position isomers Functional Group Configurational Conformational

isomers isomers isomers

E & Z isomers Isomers with

chiral centres
Structural Isomers
• Chain isomers
• Carbon chain is connected in different ways
• e.g. C5H12 (n-pentane and isopentane)

• Position isomers
• One or more functional groups are at different positions
• E.g. C3H7Cl (1-chloropropane and 2-chloropropane)

• Functional Group isomers

• Same molecular formulae, but different functional groups
• E.g. C3H8O (methoxyethane and propan-1-ol)
Stereoisomers
• Conformational isomers
• different 3D arrangements of atoms due to
rotation about single bonds
• Three main projections
• Flying wedge (or wedge and dash)
• Sawhorse
• Newman (looking down the central bond)
Conformational stereoisomers: acyclic molecules

• Conformers are related by rotations

around a single bond
• Energy barrier to rotation often
determined by steric repulsion
• Often quite small, but can be large
depending on the substituents
• Example for butane
• The terms for the alignments are often
used, so worth remembering
Conformational stereoisomers: cyclic molecules
• Remember that aliphatic cyclic molecules are non-planar
• Whenever possible they ‘buckle’ to relieve angle strain
• Remember 4-coordinate (sp3) carbon is tetrahedral and ‘wants’ bond angles of
109.5o
• The key example is cyclohexane…
 Conformers of cyclohexane
• Most stable form is the ‘chair’
conformation (A), followed by the
‘twisted boat” (B) and ‘boat’(C)
conformers.
• The forms can interconvert (‘ring flip’)
• Usually this is rapid at room temp
• Large substituents can ‘lock’ the chair
conformation

• What happens to ring substituents

when the ring changes conformation…?
 Conformers of cyclohexane
• Substituents occupy either axial or
equatorial positions...

• What happens to ring substituents

when the ring changes
conformation…?
 Conformers of cyclohexane
• The conformers of cyclohexane are important not only because of the
extensive chemistry of 6-member rings
• Glucose and all carbohydrates exist as cyclic forms in equilibrium with
their open-chain forms (cyclic forms dominate)….biological and medicinal
chemistry.

The 6-ring form is called a pyranose because a 6-member ring with 5 carbons and 1 oxygen is called pyran
Glucose also has a 5-ring form called a furanose, because a 5-member ring with 4 carbons and 1 oxygen is called furan