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stereochemistry
structural
isomers
different
bond pattern
isomers
structural
isomers ...and structural
isomers have these
atoms arranged
differently (different
bonding)...
different
bond pattern
structural isomers
OH
all these have the
same formula but are
obviously (!) very
different
cyclopentanol
C5H10O
OH O
(E)-pent-3-en-1-ol 4-methoxybut-1-ene
C5H10O C5H10O
O
HO H
3-methylbutan-2-one (S)-pent-1-en-3-ol
C5H10O C5H10O
isomers
stereoisomers have
the same atoms and
structural
the same bonds...so
same number of C– stereoisomers
isomers
C, C–H etc bonds
diastereomers
same
bond pattern
isomers
...they only differ by how these
bonds are arranged in space
(how they are orientated
relative to each other)
structural stereoisomers
isomers
diastereomers
same
bond pattern
stereoisomerism
or configurational isomerism
A C A D
B D
≠ B C
B D
≠ B C
B D
≠ B C
break
double bond remember: we cannot
rotate double bonds...so
we must break the π
A C bond, then...
B D
stereoisomerism
or configurational isomerism
A C A D
...rotate central C–C
B D
≠ B
bond...
C
break
double bond
A C A D
B D B C
rotate
single bond
stereoisomerism
or configurational isomerism
A C A D
B D
≠ B C
break reform
double bond double bond
A C A D
B D B C
rotate
single bond
diastereoisomers
MeO2C H MeO2C CO2Me
H CO2Me H H
dimethyl fumarate dimethyl maleate
trans (E) cis (Z)
mp 103°C mp –19°C
bp 193°C bp 202°C
diastereoisomers are different
compounds with different chemical
and physical properties
cyclic molecules
& diastereoisomers
cyclic molecules can exist as
diastereoisomers depending
on the relative orientation of
substituents...
Cl
Cl
relative stereochemistry
change the relative
stereochemistry to give new
diastereoisomers
Cl Cl
Cl Cl
cis-1,2- trans-1,2-
dichlorocylohexane dichlorocylohexane
(syn) (anti)
Cl Cl
Cl Cl
trans-1,2- cis-1,2-
dichlorocylohexane dichlorocylohexane
(anti) (syn)
Cl Cl
Cl Cl
cis-1,2- trans-1,2-
dichlorocylohexane dichlorocylohexane
(syn) (anti)
Cl Cl
Cl Cl
trans -1,2-
here we have TWO diastereoisomers...
cis-1,2-
dichlorocylohexane dichlorocylohexane
either both the chlorines are on the same side
(anti ) are on opposite sides
or they (syn)
Cl Cl
Cl Cl
cis-1,2- trans-1,2-
dichlorocylohexane dichlorocylohexane
(syn) (anti)
Cl Cl
Cl Cl
cisslide...which
trans-1,2- two questions arise from this -1,2-
conformation of
dichlorocylohexane each diastereoisomer is
dichlorocylohexane
(anti) preferred (easy)...and, why have I draw four
(syn)
molecules (hard)?
what will the favoured
conformation be?
cis
Cl
Cl
1Cl
2Cl
H 1Cl
2Cl
H
H
H
always
axial
one
substituent
cis
Cl
Cl
1Cl
2Cl
H 1Cl
2Cl
H
H
H
always
axial
in this example...both
one
conformations of the cis
diastereoisomer are identical...both
have one axial & one equatorial
substituent
substituent
trans Cl
Cl
2Cl
H
2Cl H
H
1Cl
H 1Cl
Cl
2Cl
X
H
2Cl H
H
1Cl
H 1Cl
equatorialfavoured
H
H
tBu
H
H
HO t
Bu
OH
H
H
tBu
H
H
HO t
Bu
OH
equatorial
largest group
favours
H
Me
tBu Me H
H tBu
H
true for all substitution patterns
(it doesn’t matter where you put
the big group it will be equatorial
equatorial
largest group
favours
decalins fused ring system found in
many natural products (such
H as steroids) can exist as two
diastereoisomers...
2 H
stereoisomers
trans-decalins
H H
H H
trans-decalin equatorial, equatorial
ring fusion
H
cis-decalin equatorial, axial
ring fusion
the one you all hate...
isomers
structural stereoisomers
isomers
diastereomers enantiomers
same
bond pattern
isomers
structural stereoisomers
isomers
a special kind of (pain)
stereosiomer...a pair of
enantiomers are identical in
always except...
diastereomers enantiomers
same
bond pattern
...an object that is
nonsuperposable on
its mirror image...
chirality in nature
chirality
in nature
chirality in nature
chirality
our hands are
mirror images...
in nature
chirality
in nature
chirality they look identical
in nature
(barring scars etc)
chirality
but can never
occupy the same
space...they are
in nature
chiral
chirality
snail shells are
either clockwise or
in nature
anti-clockwise...
in nature
clockwise snails....
windmills and
propellers are left or
right handed as are...
chiral
objects corkscrews
molecules can be left
or right handed
chiral molecules
Achiral compounds
Mirror
plane
if we take a molecule
and its...
Achiral compounds
Mirror
plane
...mirror image...and
we then start to...
Achiral compounds
Mirror
plane
rotate
rotate
Achiral compounds
Mirror
plane
rotate
it can never be
superposed...
the two isomers are called
enantiomers
H OH
Ph CO2H
(R)-(-)-mandelic acid
mp 131-133°C
HO H
Ph CO2H
(S)-(+)-mandelic acid
mp 130-132°C
9 8 7 6 5 4 3 2
but they do differ
under certain
circumstances
(otherwise why would
we care...)
except
two properties...
physical properties
α
H OH HO H
Ph CO2H Ph CO2H
(R)-(-)-mandelic acid (S)-(+)-mandelic acid
[α]23
D –153 [α]23
D +153
physical properties
α
H OH HO H
Ph CO2H Ph CO2H
(R)-(-)-mandelic acid (S)-(+)-mandelic acid
[α]23
D –153 [α]23
D +153
other chiral objects
other chiral objects
...how they interact with other chiral
objects is very different (imagine trying to
put your left foot in your right shoe...its a
tad more difficult than putting the right
foot in the right shoe)
we are chiral
we are chiral
so chiral molecules will
interact with us in
different ways...
smell
CH3 CH3
H H
CH3 H3C
(S)-limonene (R)-limonene
lemons oranges
taste
CH3 CH3
O O
H H
CH3 H3C
(R)-carvone (S)-carvone
©Patrick J. Lynch 2006 spearmint caraway
taste
CH3 CH3
O O
H H
...but these differences are
trivial compared to... CH3 H3C
(R)-carvone (S)-carvone
©Patrick J. Lynch 2006 spearmint caraway
chirality and drugs
Me Me
Me2N NMe2
Ph O O Ph
O O
Et Et
darvon novrad
painkiller cough-suppressant
chirality and drugs
Me Me
Me2N NMe2
Ph O O Ph
O O
Et Et
darvon novrad
painkiller cough-suppressant
Me CO2H Me CO2H
NH2 NH2
L-alanine D-alanine
mammalian amino acid bacterial cell wall
chirality and drugs
O O
H H
N N
O O
O N O O N O
H H
(R)-thalidomide (S)-thalidomide
(morning sickness) (teratogenic)
but we have to be very careful otherwise
we can have horrific problems such as the
limbless children born because of the use
of thalidomide
www.massey.ac.nz/~gjrowlan/teaching.html
NH2 as 2 enantiomers
1
2 =2
stereoisomers
O
H2N
N CO2CH3
H
a molecule with two carbon
HO2C atoms each with four different
aspartame
2
2 =4
groups coming off them can
exist as 4 stereoisomers
stereoisomers
if it has three atoms
(stereocentres) with 4 different
CHO
HO
OH OH
3
2 =8
stereoisomers
insulin
(monomer)
has 51 stereocentres so it can exist
as a large number of stereoisomers
51
2 = 2.25 x 1015
stereoisomers
insulin
(monomer)
51
2 = 2.25 x 1015
stereoisomers
insulin
(monomer)
so we must have a single form of
insulin so it always does the same
thing...but insulin ain’t particularly
big...
51
2 = 2.25 x 1015
stereoisomers
DNA
polymerase
this number is
meaningless to me!
342
342
>2 = >8.96 x 10102
stereoisomers
DNA
polymerase
342
but it gets
worse...consider
our genes...
342
>2 = >8.96 x 10102
stereoisomers
46 46 chromosomes
comprising of...
and each base pair is
two molecules with three
stereocentres...so we
have a possibility of...
OH N
O
O N
NH
N
HO NH2
>3 billion
base pairs
Benny Herudek 3D Hifi - High Fidelity 3d Graphics Solutions
29,000,000,000 = ∞
stereoisomers
Benny Herudek 3D Hifi - High Fidelity 3d Graphics Solutions
29,000,000,000 = ∞
stereoisomers
?
of course, why we have one enantiomer and
not its mirror image is another question
entirely...one which I will not comment on in
order to avoid offending the religious
amongst you...
what have
....we learnt?
•t h e s h a pe
of molecules
• chirality
©bioneural.net