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lct8 PDF
lct8 PDF
gjr-- 2
Isomerism
different bond
pattern
structural
isomers
diastereomers
ISOMERS
stereoisomers
same
bond pattern
enantiomers
non-superimposable
mirror images
Structural isomers
OH
OH
(E)-pent-3-en-1-ol
C5H10O
O
HO H
O
cyclopentanol
C5H10O
4-methoxybut-1-ene
C5H10O
3-methylbutan-2-one
C5H10O
(S)-pent-1-en-3-ol
C5H10O
gjr-- 3
MeO2C
H
CO2Me
dimethyl fumarate
trans (E)
mp 103C
bp 193C
less stable
steric crowding
E or trans
Z or cis
MeO2C
H
CO2Me
H
dimethyl maleate
cis (Z)
mp 19C
bp 202C
gjr-- 4
E and Z nomenclature
E-alkenes have the highest priority groups on the opposite sides
Z-alkenes have the highest priority groups on the same side
Priority rules
1. Rank atoms attached to alkene in order of decreasing atomic number
atom = Br>Cl>O>N>C>H
Atomic number = 35, 17, 8, 7, 6 & 1
2. If atoms are the same, move along substituent until a difference is found
H2
C
CH3
>
CH3
CH3
>
OH
.3. Multiple bonds are assumed to count as the same number of single bonds
C N
1 Cl
2
H3C
1 CH2CH3
C C
CH3
(Z)-2-chloro-3methylpent-2-ene
N C
1CHO
HO2C 1
C C 2
2
Ph
CH2OH
(Z)-3-hydroxymethyl-4-oxo-2phenylbut-2-enoic acid
C N
N C
N
1CH OH
C2
2
C C 2
1
Br
CH2CH3
(E)-2-bromo-3(hydroxymethyl)
pent-2-enenitrile
H3C
2
H3C
O
2 CH
3
C C
C6H5
(E)-3-methyl-4phenylpent-3-en-2-one
gjr-- 5
Cl
Cl
Cl
trans-1,2dichlorocylohexane
(anti)
Cl
Cl
trans-1,2dichlorocylohexane
(anti)
Cl
cis-1,2dichlorocylohexane
(syn)
2Cl
2Cl
H
H
both conformations have one axial
substituent & are identical
Me
2Cl
1Cl
2ClH
1Cl
H
bulky group equatorial
favoured
1Cl
H
tBu
Me
H
H
tBu
tert-butyl group
rarely is axial
gjr-- 6
Decalins
H
H
H
H
trans-decalin
H
equatorial, equatorial
ring fusion
H
cis-decalin
equatorial, axial
ring fusion
gjr-- 7
Chirality
Mirror image
Non-superimposable
gjr-- 8
Enantiomers
This form of stereoisomerism arises from a lack of symmetry
The molecule & its mirror image are different
The molecule & its mirror image are known as enantiomers
Achiral
Chiral
Mirror
plane
Mirror
plane
rotate
For those of a sick & twisted disposition more info on chirality & stereochemistry
can be found at my website: http://www.massey.ac.nz/~gjrowlan/teaching.html
gjr-- 9
Enantiomers II
Most common form of chirality has a carbon atom with 4 different groups
attached & is called central chirality
Me
Me2N
H
Ph O
O
Et
darvon
painkiller
Me
N
H
O
N
O
H
(R)-thalidomide
(morning sickness)
CO2H
N
NH2
Me
nicotine
toxin / stimulant
L-alanine
Ph
PPh2
Ph2P
PPh2
(R)-(+)-BINAP
(R)-2-(diphenylphosphino)-1-(2-(diphenyl
phosphino)naphthalen-1-yl)naphthalene
M-[8]helicene
Fe
(R)-2-phenyl-1(diphenylphosphanyl)
ferrocene
gjr-- 10
OH
Ph
CO2H
(R)-(-)-mandelic acid
131-133C
23
[]D
153
light
source
light ()
polariser
sample
cell length l (dm)
plane
polarised light
reading
HO
Ph
CO2H
(S)-(+)-mandelic acid
131-134C
20 +154
[]D
Chiral compounds rotate the plane of polarised light (hence optical isomers)
As most biological systems are chiral, enantiomers can have different effects
O
H
(R)-carvone
spearmint
H
(S)-carvone
caraway
H
(S)-limonene
lemons
H
(R)-limonene
oranges
gjr-- 11
O
OH
HO
NH2
NH2
NH
Two enantiomers
differ by absolute configuration
O2N
CO2Me
CO2Me
enantiomers
trans
epoxide
mp = 141C
O2N
diastereoisomers
enantiomers
different mp
cis
epoxide
mp = 98C
O2N
CO2Me
O
CO2Me
O
gjr-- 12
Me
NH2
alanine
HO2C
H
N
HO2C
NH2
phenylalanine
NH2
histidine
O
H2N
N
H
CO2CH3
HO2C
Insulin is made of 2 peptide chains - 1x30 amino acids & 1x21 amino acids
Potentially 2.25 x 1015 diastereoisomers
A relatively small protein is ribonuclease at 124 amino acids or
Potentially 2.13 x 1037 diastereoisomers
gjr-- 13
Chiral drugs
Et
H
N
N
H
OH
OH
Et
OH
H
N
N
H
Et
NH
Me
()-propanolol
-blocker for heart disease
OH
(R,R)-enantiomer
causes blindness
Ethambutol
tuberculostatic (anti-TB)
OH
Me
Et
HN
Me
Me
OH
(+)-propanolol
contraceptive
O
N
O
OH
N
H
N
H
OH
N
S
(S)-timolol
high blood pressure
N
S
(R)-timolol
glaucoma
gjr-- 14
Overview
What's next?
A brief look at spectroscopy in many of its glorious forms
Starting with NMR or nuclear magnetic resonance spectroscopy
An idea of what information this tells us about protons in a molecule