Organic Chemistry II

Chapter 5 Stereoisomers

I. Introduction
A. Mirror Images may not be Superimposable
1) Pair of gloves 2) Shoes
3) Your image in a mirror 4) Screws

B. Isomer Types
1) Isomer = same molecular formula, different structure
a) Constitutional Isomers: different order of connectivity
b) Stereoisomers: same connectivity, different spatial orientation
i. Diastereomers: stereoisomers that are not mirror images
ii. Enantiomers: non-superimposable mirror images
2) Conformations = stereoisomers that can rapidly interconvert by rotation
II. Chirality = describes objects not superimposable with their mirror image
A) Products of Radical Bromination of Butane

1) 2 products are produced

2) Are they mirror images? Are they Superimposable?
3) Chiral, Enantiomeric products; each enantiomer is one of a pair
4) (Achiral = is superimposable with mirror image)
5) One carbon is bonded to 4 different: Me, Et, H, Br
a) These carbons are always chiral
b) Asymmetric carbon
c) Stereocenter A A
D D
C B B C
B) Molecular Symmetry
1) Plane of Symmetry
a) Bisects molecule to give mirror image halves

H
b) Chiral molecules have zero planes of symmetry
c) Methane has 6 planes of symmetry: Achiral H
d) CHFClBr has no planes of symmetry: Chiral H
H
2) When is Chiral not Chiral?
a) Rapid structural changes give an Average Symmetry
b) A given structure must be room temperature isolatable
c) Conformational changes
i. Butane conformations are chiral, but Butane is achiral
ii. cis-1,2-dimethylcyclohexane has achiral intermediate
III. Optical Activity
A) How do you tell Enantiomers Apart?
1) Most Physical Properties are identical: mp, bp, density, etc…
2) Enantiomers interact differently with plane polarized light
3) Each enantiomer of a pair rotates the light in a different direction

a) Dextrorotatory = clockwise rotation (+)
b) Levorotatory = counterclockwise rotation (-)
4) Descriptions: Optical Activity, Optically Active, Optical Isomers

a
a 
B) Using a Polarimeter to calculate Optical Purity to
1) a, the rotation angle, depends on cell length, T, solvent, etc…  
a) L = length in dm (0.1 m) c = concentration in g/ml lc
b) Specific rotation can be compared; constant for given molecule
2) Pure enantiomer has maximum a (+23o or –23o)

3) Racemic Mixture = 50%/50% mixture of enantiomers has a = 0
4) Anywhere in between will have rotation between these values
5) Enantiomeric Excess = %Optical Purity = how much more of one
enantiomer than the other
 a  
%Optical Purity   observed x100 
 a  
6) Exercise 5-7 75% optical purity, [a] = 23.1o, what is [a]observed?
ao
0.75   0.75a  a o  (0.75)( 23.1o )  17.33o
a
7) How much of each enantiomer is present? NOT 75%/25%

12.5% (+) / 12.5% (-) and 75% (+) Total = 87.5% (+), 12.5% (-)
IV. R,S Rules
A) Absolute Configuration
1) +/- tell us the interaction of light, not the exact structure of enantiomers
A A
D D
C B B C
2) X-Ray Crystallography gives us Absolute Configuration

a) Crystals are regularly arranged solid forms
b) They Diffract X-rays regularly, so we can tell what atom is where
c) X-Ray and Polarimetry lets us match +/- with a specific structure
d) Similar molecules usually have same +/- correlation
B) R/S Labels
1) Cahn-Ingold-Prelog System assigns name to each enantiomer
2) Arrange substituents with lowest priority in back
a) Clockwise arrangement high-to-low = R (rectus = right)
b) Counterclockwise = S (sinister = left)
R enantiomer S enantiomer
3) Write the name: R-(+)-chloroflouorobromomethane
4) Racemic Mixture: R,S-(+/-)-chlorfluorobromomethane
5) Rules for assigning priority (Try Exercise 5-8 thru 5-10)

a) Highest Atomic Number: Br > Cl > F > H
b) For equal atomic number, look at what is attached
i. Only look at one level at a time
ii. If second level identical, then go to third level
c) Treat double and triple bonds as 2 or 3 single bonds to that atom
H H
a a
ClCH2 c Cl,2H > C,2H > 3H (CH3)2CH c 2C,H > C,2H > 3H
CH3CH2 CH3 CH3CH2 CH3
b
b
H
H a
a HC C b
HOCH2CH2 CH3CH2 CH CH2
CH3CH2 CH2CH2CH3
c
c b

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Chapter 5 Stereoisomers

1) 2 products are produced

a) Bisects molecule to give mirror image halves

3) Each enantiomer of a pair rotates the light in a different direction

4) Descriptions: Optical Activity, Optically Active, Optical Isomers

2) Pure enantiomer has maximum a (+23o or –23o)

7) How much of each enantiomer is present? NOT 75%/25%

2) X-Ray Crystallography gives us Absolute Configuration

5) Rules for assigning priority (Try Exercise 5-8 thru 5-10)

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