Essential Organic Chemistry

Paula Yurkanis Bruice

Chapter 8

Isomers and Stereochemistry

William Setzer, Bernhard Vogler, Mary Setzer

University of Alabama - Huntsville
 Review of Isomerism
 Isomers – Different compounds that have
the same molecular formula.
 Constitutional Isomers – differ because
their atoms are connected in a different
order.
CH3CH2-O-CH2CH3 vs. CH3CH2CH2CH2OH
Constitutional Isomers
 8.1 Cis-Trans Isomers
 Differ in the arrangement of their atoms in
space (cannot interconvert)- Alkenes.
 8.1 Cis-Trans Isomers
 Cyclic structure.
 8.2 Chirality
 Chiral –
Nonsuperimposable on its
mirror image.
 Achiral – Superimposable
on its mirror image.
 If a molecule (or object) has
a mirror plane or an
inversion center, it cannot be
chiral.
 Chiral or Achiral?
 cis-1,3-dimethylcyclopentane

achiral

mirror plane
 Chiral or Achiral?
 trans-1,3-dimethylcyclopentane

chiral
 Chiral or Achiral?
 1,1-dimethylcyclohexane

achiral
 8.3 Asymmetric Centers

 An asymmetric center is an atom that

is bonded to four different groups.
 Chiral or Achiral?
Asymmetric
 2-butanol center

chiral mirror image

 Chiral or Achiral?
 2-bromopropane

achiral
8.4 Isomers with One Asymmetric Center
8.4 Isomers with One Asymmetric Center
 Enantiomers
 A chiral compound and its mirror image are
called enantiomers.
 2-butanol:

enantiomers
 Enantiomers
 Asparagine: mirror
plane
O OH HO O
C C

H2N C H H C NH2

CH2 CH2
C C
H2N O O NH2
L-asparagine D-asparagine
(from asparagus) (from vetch)
bitter taste sweet taste
enantiomers
8.5 Drawing Enantiomers
8.6 Naming Enantiomers: The R,S System
 Absolute Configuration
 R and S
• Look down the bond from the chiral carbon to
the smallest group:

CH 2CH3 1 2
OH HO CH2CH3
H C = C
CH3 CH3
3
 Absolute Configuration
 R and S
• Look down the bond from the chiral carbon to
the smallest group:

CH 2CH3 1 2
OH HO CH2CH3
H C = C
CH3 CH3
3
 Absolute Configuration
 R and S
• Assign priorities to the remaining groups based
on atomic numbers.
• Clockwise (highest to lowest priority)  R
• Counterclockwise  S
CH 2CH3 1 2
OH HO CH2CH3
H C = C
CH3 CH3
3
 Absolute Configuration
 R and S
• Assign priorities to the remaining groups based
on atomic numbers.
• Clockwise (highest to lowest priority)  R
• Counterclockwise  S
CH 2CH3 1 2
OH HO CH2CH3
H C = C
CH3 CH3
3
(R)-2-butanol
 Absolute Configuration
 Assign priority:
• Atomic number of atom directly bonded.
• If the same atom is bonded, go to the next atom,
etc.
• Groups containing multiple bonds are treated as
though multiple atoms were attached:
N C
C O = C O C N = C N
O C N C
 Absolute Configuration
 Determine the absolute configuration of the
following compounds:
3 1
H3C 4 F 4
H H
C C
Cl CH
Br S 2 D R 2 3
1 3

2 O
(CH3)2CHCH2 4
1
H
H C 4
C H

S Cl C
CH3CH2CH2CH2 1 C N
3 CH3CH2 R 2
3
 Absolute Configuration
 Determine the absolute configuration of the
following compounds:
CH3 CH3
1 2
CH3O CH 4 CH3O CH 4
H H
C C
2
S CH3 1
R CH3
CH3CH2 CH 3 CH3CH2 CH 3

OH OCH3
1 2
CH2=CH 4 CH2=CH 4
H H
C C
2
S CH3 S C CH
CH3CH2 3 (CH3)2CH 1
3