Chapter 5. Stereoisomerism.
Constitutional Isomers -- Compounds with the same ____________________ ________________ but the atoms are
_____________________________ ___________________________.
Examples:
Stereoisomers -- Isomers with the same _________________________ (that is, the atoms are _________________
the ____________________) but a different ___________________________________ arrangement of atoms.
One type of stereoisomerism:
Examples: cis-1,2-dimethylcyclohexane trans-1,2-dimethylcyclohexane
cis-2-butene trans-2-butene trans-3,4-dimethyl-3-heptene 2-methyl-2-butene
Cis-trans stereoisomerism results because of ____________________________________________________________
In order for an alkene to exhibit cis-trans isomerism, each of the doubly-bonded carbon atoms must
Which of the following compounds can exist as cis-trans stereoisomers?
CH3CH2CH=CHCH2CH3 CH3CH2CH=C(CH3)2
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Chirality
Consider the mirror images of sp3 hybridized carbon compounds:
CH3X
CH2XY
CHXYZ
chiral – A chiral molecule is _________________________________ on its ________________ _________________
• Generally, chiral molecules do not have a ___________________________________________________.
• “chiral” - _________________________________;
• ________________________________ vs ____________________________________
achiral – An achiral molecule _______ _____________________________ on its _____________ ________________.
• An achiral molecule has a ______________________________________________
enantiomers – Stereoisomers of a ___________________ substance that have a _______________ _______________
relationship.
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chirality center -- Also called _____________________ center or __________________________________.
• A chirality center is a _________________________ atom attached to _________________________________
Question #1: Identify the chirality centers in the following molecules:
CH3 CH3
CH3
CH3 CH CH3 CH3 CH CH2 CH3
Br Br Br CH3
Question #2: Identify the chirality centers in the following molecules:
1-pentanol 2-pentanol 3-pentanol
Question #3: Which of the following compounds is/are chiral?
I. 1,1-dichloropentane
II. 1,2-dichloropentane
III. 3-chloropentane
IV. 2,3-dichloropentane
a) II
b) II and IV
c) IV
d) II, III and IV
e) I and III
Question #4: Draw the two enantiomers of alanine, CH3CH(NH2)COOH
Rules for Designating Configuration of Chirality Centers
1. ____________________ all four groups attached to the chirality center, using the Cahn-Ingold-Prelog rules.
• The number one priority rule: ____________________ ____________________
• You must look at __________ ______________ at a time, to the ___________ _______________ of difference.
• Remember to count ________________________________________.
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2. With the lowest priority substituent ____ _____________,
if the order of priority is clockwise, the configuration is _______
if the order of priority is counterclockwise, the configuration is _____.
Question #5. Determine which substituent from each pair below has the higher priority.
1. -CH3 -H
2. -CH2Cl -CH2CH2CCl3
3.
4.
5. –CHO –CH2OH
Question #6: Determine the R,S configuration of each chirality center below.
OH CH3 CHO
C C C
H H H3C CH2OH
CH3 CH2CH3
Br HO H
C
H3C COOH
H3CH2C
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Optical Activity
Electromagnetic radiation – a form of _______________ that travels through space at the _______________________
• Electromagnetic radiation is characterized by _______________________ ________________________ and
_____________________________ fields
• The ________________ and ___________________ fields oscillate in planes ___________________________
to each other.
Organic molecules that rotate plane-polarized light are said to be ____________________ ___________________.
As an example, consider a solution of -D-glucose:
If rotation is to the left, the compound is called _______________________________ or _________ or __________.
If rotation is to the right, the compound is called ______________________________ or _________ or __________.
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The observed rotation, ________________ or ________________, depends on:
The specific rotation, _______________________, is used as the literature value. This value can be replicated since it
takes into account
Question #7: When 15.0 g of sucrose is dissolved in 75.0 mL of water and placed in a sample cell 10.0 cm in length, the
observed rotation is +13.26° (using the D line of sodium at 20° C). What is the specific rotation of sucrose?
Consider the two enantiomers of lactic acid, CH3CH(OH)COOH:
This illustrates two principles:
1. Enantiomers rotate plane-polarized light
2. (R) and (S) are not
A necessary but not sufficient condition for an organic solution to rotate plane-polarized light is that it contain
When does a solution of chiral molecules not rotate plane-polarized light?
A solution containing a single enantiomer is said to be
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Racemic mixture:
A solution containing both enantiomers in unequal amounts will be ________________________ _________________.
enantiomeric excess:
Question #8: A. What is the percent enantiomeric excess of a sample of carvone that exhibits a specific rotation of
+10°? (Given: the specific rotation of (R) carvone is -61°.) B. Which enantiomer is in excess? C. What is the relative
percentage of each enantiomer in this solution?
Fischer Projections
Key Point: The horizontal groups _________________________________________________________
Question #9: Determine the R,S configuration for each chirality center below:
H CHO
H3C OH H OH
CH2CH3 CH2OH
Question #10: The carbohydrate D-threose has the following Fischer projection:
CHO
HO H
H OH
CH2OH
Assign R or S configuration to the two chirality centers in D-threose.
a) (2R, 3R)
b) (2R, 3S)
c) (2S, 3R)
d) (2S, 3S)
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Question #11: Which of the following structures is/are identical to the Fischer projection shown?
Br Br Br Br
Br H A. B. C. D.
Br H Br Br Br
Br
Molecules with Two Chirality Centers
2n rule:
How many stereoisomers of 3-chloro-2-butanol exist? Draw the Fischer projections of each of these.
How many stereoisomers of 2,3-dichlorobutane exist? Draw the Fischer projections of each of these.
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enantiomers:
diastereomers:
meso compounds:
Question #12: Which of compounds 1,2 and 3 will have only 3 stereoisomers?
Cl
OH
Cl
CHCHCOOH
1) 2) 3)
Cl
OH Cl
a) 1 only b) all
b) 1 and 2 c) none
Question #13: Which of the compounds below exists as only three stereoisomers?
a) 1,4-dibromobutane
b) 2,3-dibromobutane
c) 2,3-dibromopentane
d) 1,1-dibromocyclopentane
e) 1,4-dibromocyclohexane
Question #14: Which of the following is/are meso?
These examples illustrate two principles:
1. A meso compound with two chirality centers will have
2. If any conformation has
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Question #15: Consider the molecule below:
CH 3
H OH
H Br
CH 3
Which of the structures shown is a diastereomer of this molecule?
OH CH3 H H H
H3C H HO H HO CH3 H3C OH HO CH3
Br CH3 H CH3 H Br Br H H3C Br
H Br CH3 CH3 H
A B C D E
Tartaric Acid:
Compare the physical properties of the 3 stereoisomers of tartaric acid:
Stereoisomer melting point []D density solubility
(g/100 mL H2O)
This illustrates several important principles:
1. Two enantiomers exhibit
2. Two diastereomers have
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3. Meso compounds are
4. A racemic mixture has
Resolution of Enantiomers –
Since enantiomers have the same ______________________ ______________________, they cannot be separated
using traditional methods such as __________________________ . Our textbook suggests three ways to resolve
enantiomers.
1.____________________________________________________________
Louis Pasteur, in 1847, took a racemic mixture of tartrate salts:
After recrystallizing this mixture, Pasteur noticed that the solid consisted of
which he then __________________________ ___________________________. This is generally not a practical way to
separate enantiomers.
2.____________________________________________________________
When a racemic mixture reacts with a _________________ ______________________ of another compound, the
resulting product may produce a pair of _______________________, which can be
3.________________________________________________________
