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Stereoisomers
Chirality
(R) and (S) Nomenclature
Depicting Asymmetric Carbons
Diastereomers
Fischer Projections
Stereochemical Relationships
Optical Activity
Resolution of Enantiomers
Stereochemistry
Stereochemistry:
The study of the three-dimensional
structure of molecules
bonding sequence
Stereoisomers:
same molecular formula, same bonding
Stereochemistry
CH3
O
CH3
CH3
O
H3C
CH2
H
CH2
Caraway seed
O
H
H2C
CH3
spearmint
Stereochemistry
The properties of many drugs depends on their
stereochemistry:
HN
O
O
CH
CH3
NH3NH
O
NHCH3
Cl
HN
Cl
Cl
O
CH3NH
Cl
(S)-ketamine
(R)-ketamine
anesthetic
hallucinogen
Stereochemistry
Enzymes are
capable of
distinguishing
between
stereoisomers:
Types of Stereoisomers
Two types of stereoisomers:
enantiomers
two compounds that are nonsuperimposable
diastereomers
Two stereoisomers that are not mirror
Chiral
Enantiomers are chiral:
Chiral:
Not superimposable on its mirror image
Many natural and man-made objects are chiral:
hands
scissors
screws (left-handed vs. right-handed threads)
Right hand threads
slope up to the right.
Chiral
Some molecules are chiral:
Asymmetric
(chiral) carbon
Asymmetric Carbons
The most common feature that leads to
In general:
no asymmetric C
1 asymmetric C
> 2 asymmetric C
usually achiral
always chiral
may or may not be
chiral
Asymmetric Carbons
Example: Identify all asymmetric carbons
present in the following compounds.
Br
OH H
H3C
CH3
CH2CH3
H
H
Br
Br
Br
H CH
3
Achiral
Many molecules and objects are achiral:
identical to its mirror image
not chiral
Cl Cl
Cl Cl
Cl
Cl
compound:
an achiral compound that contains chiral
centers
often contains an internal mirror plane of
symmetry
HO2C
HO
H
CO2H
OH
H
H Br
CH2CH3
C
H3CH2C
CO2H
H
OH
HO
H
Br
O
C OHF
C H
CH3
H
H3C
H
C
F
Cl
H
of symmetry?
Yes:
achiral
No:
If mirror image is nonsuperimposable, then its chiral.
If mirror image is superimposable,
then its achiral.
mobile.
rapidly converting from one conformation to
another
Br
Br
CHthe
3
Example: Identify
following molecules as
chiral or achiral.
CH3 C CH2CH3
Cl
CH3CHCH2CH2CH3
CH3
Br
Br
Cl
CH3
CH3CH2
CH3CCH2CH3
Cl
Br
H
Br
H
trans-1,3-dibromocyclohexane
CH2CHethylcyclohexane
3
H
Br
H
C
Br
CH2CH3
CO2H
CO2H
C
H3C
H
NH2
Natural alanine
(S)-alanine
H
H2N
C
CH3
Unnatural alanine
(R)-alanine
C 2
H3 C
OCH2CH3
H
4
CH3
C H4
NH2
1 F
2
Example priorities:
I > Br > Cl > S > F > O > N >
1H
13C
>
12C
chain as tiebreakers.
2 CH CH Br
2
2
C
3 CH CH
2
3
H4
CH(CH3)2
1
C Y
(R) and (S)
Nomenclature
C Y
Y
Y
Treat double and
triple bonds as if both atoms
C Y
Y
or triplicated:
O in the bondC were
C
C Yduplicated
C
C
OH
C Y
CH2OH
C
Y
O 2 H
Y C
1
C C OH
4 H CH2OH
3
Y
Y
C
Y
C
C O
Y
C Y2
O C H
C
C 4 HY
C
Y C
OH
CH2OH
Y3
Y
Y
C
C
Y
C
Y
(R) configuration
(S) configuration
CH3)2
CH3
CH3
C
CH2C
CH3
CH2CH3
OHH
OH
H3
Br
C
CH3
H
C
CH3 Br
CO2H
CH(CH3)2
Br
CH3
COH
CH2C
H OH
CH2CH3
Br
H
CH3
Br
CH3
CH3
H Br
H3C
H
Cl
CH3
(2S, 3S)-2-bromo-3-chlorobutane
Cl
CH3 C* CH2CH2CH3
H
Step 2: Assign priorities to each group attached to
the asymmetric carbon.
1
Cl
3 CH C
3
H 4
2
CH2CH2CH3
Depicting Structures
with Asymmetric
Cl
Carbons
CH3 C
CH2CH2CH3
Cl
CH3 C
C
CH
H 2CH2CH3
Cl
H
C
CH3 CH2CH2CH3
HO2CCH
CH3
CH2CH(CH3)2
O
N
CO2H
CHCH2SH
CH3