218 CHAPTER 5 Stereoisomerism

SKILLBUILDER REVIEW
5.1 LOCATING CHIRAL CENTERS

STEP 1 Ignore sp2 - and STEP 2 Ignore STEP 3 Identify any carbon
sp-hybridized centers. CH2 and CH3 groups. atoms bearing four different groups.

Try Problems 5.4–5.6, 5.33b

5.2 DRAWING AN ENANTIOMER

Either place the mirror or place the mirror on or place the mirror
behind the compound... the side of the compound... below the compound.

NH2

NH2
NH2 H2N
NH2 NH2

Try Problems 5.7, 5.8, 5.32, 5.33a, 5.38a–c,e

5.3 ASSIGNING CONFIGURATION

STEP 1 Identify the
four atoms attached to
the chiral center and
prioritize by atomic
number.
STEP 2 If two (or more) atoms STEP 3 Redraw STEP 4 Rotate STEP 5 Identify direction
are identical, make a list of the chiral center, molecule so that of 1-2-3 sequence:
substituents and look for the first showing only the the fourth priority clockwise is R, and
point of difference. priorities. is on a dash. counterclockwise is S.

O C
O O 1 4
? ? H
O 2 3 1 4
HO H 2 3
O HO
H N H 1 4 2 3
4 H N H
1 Counterclockwise=S
H
H

Try Problems 5.9–5.10, 5.31, 5.34, 5.35, 5.39a–e,g, 5.50

5.4 CALCULATING SPECIFIC ROTATION

EXAMPLE Calculate the specific rotation STEP 1 Use the following equation: STEP 2 Plug in the given values:
given the following information: α +1. °
pecific rotation = [α] = =
c×l 0.03 g"m × 1.00 m
water = +66.3

Try Problems 5.11–5.14, 5.41, 5.42, 5.49, 5.54c, 5.56

5.5 CALCULATING % ee

EXAMPLE Given the following STEP 1 Use the following equation: STEP 2 Plug in the given values:
information, calculate the enantiomeric | o serve α |
excess: ee = × 100 = × 100 =8
| α of pure enantiomer | 3

mixture.

Try Problems 5.15–5.18, 5.40, 5.43, 5.54a,b

 SkillBuilder Review 219

5.6 DETERMINING THE STEREOISOMERIC RELATIONSHIP BETWEEN TWO COMPOUNDS

STEP 1 Compare the STEP 2 If all chiral centers have opposite configuration, the
configuration of each chiral compounds are enantiomers. If only some of the chiral centers
center. have opposite configuration, then the compounds are diastereomers.

OH OH
OH OH

Enantiomers

Try Problems 5.19, 5.20, 5.36a–g, 5.44b, 5.53b–d, 5.63

5.7 IDENTIFYING MESO COMPOUNDS

Draw all possible stereoisomers and then look for a plane of symmetry in any of the drawings.
Example The presence of a plane of symmetry indicates a meso compound.

OH
OH OH OH OH
+
OH
OH OH OH OH

Enantiomers Meso

Try Problems 5.24, 5.25, 5.37, 5.51, 5.52, 5.55, 5.57a,b,d,f–h, 5.61, 5.62

5.8 ASSIGNING CONFIGURATION FROM A FISCHER PROJECTION

EXAMPLE Assign STEP 1 Choose one horizontal STEP 2 STEP 3 Rotate STEP 4 Assign
the configuration line and draw it as a wedge. Assign so that the fourth configuration.
of this chiral center. Choose one vertical line and priorities. priority is on
draw it as a dash. a dash.

O OH O OH 1
2 1
3 2
H OH H OH 4 1 3 2
4
CH2OH CH2OH 3 4
R

Try Problems 5.26, 5.27, 5.39f, 5.44a, 5.46c, 5.47, 5.48, 5.57c,e, 5.58–5.60

5.9 ASSIGNING THE CONFIGURATION OF A DOUBLE BOND

STEP 1 Identify the two groups STEP 2 Repeat step 1 for the other vinylic STEP 3 Determine whether the
connected to one vinylic position and then position, moving away from the double priorities are on the same side (Z )
determine which group has priority. bond and looking for the first point of difference. or opposite sides (E ) of the double bond.

HO
HO HO

Try Problems 5.29, 5.30, 5.68

220 CHAPTER 5 Stereoisomerism

PRACTICE PROBLEMS Note: Most of the Problems are available within

an online teaching and learning solution.
,

5.31 5.36

Br
O

O OH OH O
O Br
N N OH
H

F
OH OH
5.32 Atropa belladonna

Cl Cl Cl Cl

CH3 OH OH
N

5.37

Me
OH Cl OH Me
H
O
O
OH OH Cl
OH

5.33
Taxus brevifolia
O HO OH
O O OH
5.38
H
O N O
Cl OH
H O Cl F
O O
OH O
OH
O
O O H

H OH
OH OH Cl Cl OH O
H OH
HO H
CH3 Me Me
5.34
5.39

Cl

O Et OH NH2

Me
HO
5.35
H F

Et O
Cl

Me
H OH
P Cl O
HO H
Me
 Practice Problems 221

5.40 5.47

ee
O OH O OH O OH

5.41 H OH HO H HO H
HO H HO H H OH

OH H OH HO H HO H

HO CH2OH CH2OH CH2OH

5.42 S + 5.48

5.49

5.43 L +
L 5.50 R

+ ee

5.44
R
S
O H O H

HO H HO H Cl Cl
H OH HO H
CH2OH CH2OH Cl Cl

5.51

5.45

Cl
H3C Br H Me
OH H
HO Br Me H
Cl Cl Cl Cl
H CH3 Cl

5.52 cis
OH OH

5.53

Cl Cl
Me Me
5.46 H Cl Cl H
HO H HO H
Me Me
meso
image.

CH3 CH3 Et Et
H OH HO H H OH HO H
A D HO H H OH HO H H OH
D B C A H OH HO H H OH HO H
C B CH3 CH3 Me Me
222 CHAPTER 5 Stereoisomerism

5.54 S + + OH
Cl Cl
R
−
OH OH
R
ee OH OH

5.55

OH 5.56
+
Cl

OH

INTEGRATED PROBLEMS
5.57 5.60
− OH
CH3 OH O OH O
OH Et
HO H HO
H Me Me Cl OH HO OH
H OH
Me H H Me OH OH OH
OH H CH3
OH O

O
H HO OH
CH2CH3 OH OH
HO H H H
H OH
H CH3 5.61
CH2OH CH3

5.62

OH
HO OH

5.58
5.63

CH3 Et Et Et
H OH H OH HO H H H

HO H HO H H OH H Me
H OH Me
H OH HO H
CH3 Me Me
5.64
Me Me
H Cl Cl H CH3
H3C
HO H HO H
H
Me Me

5.65
5.59 O
H3C CH3
meso O

5.66
 Integrated Problems 223

against canine osteosarcoma. .

1.
O O
R
OH N
NH H NH H
O H
H N O N O
O O
O H O
N O O

O O 1 2

5.67 5.71

S
H H
R enantiomer is the main
H

O
O O
O O
O Catalyst
EtO OEt OEt
(Cu or Cu form), EtO
+
Base, NO2
NO2 Solvent

5.68
cell proliferation

S
inhibitor.10 R

O OH % ee OF % YIELD OF
SOLVENT (S)-PRODUCT PRODUCT

55
33
HO O
3 55
3
5.69 Over
44

stereoisomers. 5.72

CH2OCOCH3

OH
COOH
14
H3C correct
O CH3
H3C
N
11-Acetoxy-△9-tetrahydrocannabinoic acid A N

OMe
5.70 One protease inhibitors
N N
H
2 R
1. Reported structure of (+) ‒ trigonoliimine A
224 CHAPTER 5 Stereoisomerism

5.73 5.75

OH H
One of the
H OH

O
O
O
Catalyst
N + 5.76
O
O
O O COOH
H
H OH CH3
N HO H H
H OH CH3
O H + Stereoisomers
COOH H

CH3 H H
H Br H CH3
cis
Br H H CH3
CH3 H H

Problems 5.74–5.76 follow the style of the ACS organic

chemistry exam. For each of these problems, there will be
one correct answer and three distractors.

5.74

H CH3
HO
N

R S Z

CHALLENGE PROBLEMS
17
5.77 5.78

16 O

H
O OCH3
O

O OH
H
OH
H2N