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CH 5. Stereochemistry
CH 5. Stereochemistry
Isomers:
Different compounds that have the same
molecular formula (composition) but different
connectivity. Two classes:
- Stereoisomers:
same molecular formula, same bonding
sequence, but different arrangement in space.
Structural Isomers in Alkanes
CH4 1 C8H18 18
C2H6 1 C9H20 35
C3H8 1 C10H22 75
C4H10 2 C15H32 4,347
C5H12 3 C20H42 366,319
C6H14 5 C40H82 62,491,178,805,831
C7H16 9
Structural Isomers in Alkanes
n-Butane:CH3(CH2)2CH3 Isobutane:(CH3)3CH
n-Pentane: CH3(CH2)3CH3
superimposable nonsuperimposable
Chiral molecules & Chirality Center
Cl Cl Cl Cl
Practices on Asymmetric Carbons
H OH H H
Br CH3 CH2CH3
H C *C C C H H H
* H
H H H H H CH H3C
Br 3 * *
OH
* *
CH3CHCOOH * * *
Fischer Projections:
O OH OH
* *
CH-CH-CHCH2OH
* *
Internal Plane of Symmetry
HO2C CO2H
H
O
C C F C OHF C
HO H Cl
H OH HO C H F H
Chiral vs. Achiral
of symmetry?
– Yes: achiral (meso)
– No: chiral
H Br
Chiral vs. Achiral
Br
Practice: Identify the following molecules Has
chiral or achiral. CH3
Cl CH3
CH3 C CH2CH
CH 3CH2 H
Br
CH3CCH2CH3 C C
3
CH3CHCH2CH2CH3 H
Cl Br CH2CH3
Cl
H Br Br
Br
Br H H H
cis-1,2-dibromocyclobutane
CH3trans-1,2-dibromocyclobutane
CH CH
Types of Stereoisomers
priorities: I > Br > Cl > S > F > O > N > 12C > 1H
CH(CH3)2 > CH2CH2Br > CH3CH2
1 3
Cl CH3
2 CH CH Br
2 2
3 C 2
C H4
H3C C H4
OCH2CH3 F NH2 3 CH CH
H 1 2
3 2
CH(CH3)2
4 1
Remember the periodic table of elements
Enantiomers and (R) & (S) Nomenclature
1 1
4
4
3 3
2 2
(S)-lactic acid (R)-lactic acid
2
CH2CH3 Although we have clockwise arrow, (we suppose to
name it (R), but because the H is in front, so we
1 C 3 reverse the name to (S).
Br CH3
H4 (S)-2-bromobutane
Enantiomers and (R) & (S) Nomenclature
When naming compounds containing multiple
chiral atoms, you must give the configuration
around each chiral atom:
position number and configuration of each
chiral atom in numerical order, separated by
commas, all in ( ) at the start of the
compound name
Some of these
isomers are
enantiomers and
some of them are
diastereomers. We
may find some of
them identical !!!!!
Structures (1 ,2) and (3 ,4) are enantiomers (note each S became R and vice versa)
Structures ( 1, 3) ,( 1,4) ,(2,3) and (2,4) are diastereomers (note one S became R, and the
other dose not change)
How many stereoisomers?
Structures (1,2) are identical (meso compound) because the molecule contains internal
plane of symmetry. Thus we just have 3 isomers not four.
Structures (3 ,4) are enantiomers.
Structures ( 1, 3) ,( 1,4) and (2,4) are diastereomers.
How many stereoisomers?
Ex1 Ex3
Ex2
COOH
H * OH A meso compound,
contains 2 or more
H * OH
COOH stereocenters and a
(2R,3S)-tartaric acid plane of symmetry
Importance of Stereochemistry
O O O O
NHCH3 CH CH3
NH3NH CH3NH
Cl Cl Cl Cl
(S)-ketamine (R)-ketamine
anesthetic hallucinogen
Properties of Enantiomers
1. Same boiling point, melting point, density
2. Same refractive index
3. Different interaction with other chiral molecules e.g.Enzymes
Enzymes are capable of distinguishing between stereoisomers:
Plane-Polarized
Light through an
Achiral Compound
Plane-Polarized
Light through a
chiral Compound
Specific Rotation, [α]
[α] = α / cl
a = observed rotation, c = concentration in g/mL
l = length of tube in dm
Dextrorotary designated as d or (+), clockwise rotation
Levorotary designated as l or (-), counter clockwise rotation