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Me H Me CO2H
H CO2H HO2C Me H CO2H H Me
H H H H
CO2H CO2H CO2H CO2H
Me Me Me Me
Me
OH
Me
Me Me
HO HO
Et
OH Et
Et Et
H H
H H 0
60
H C C
Wedge-and-dash C C H
H
structures H H
H H
H
H
H H
600 H H
H H
Sawhorse H
projections
H H
H H
H HH
H H 600
Newman H
projections H H H H
H
H
Torsion or Dihedral angle
• The rotational barrier is (12 kJ/mol) small enough to allow the conformational isomers
to interconvert million of times per second
Conformations and Conformers
D
B
A “gauche”
B “ Partially eclipsed”
C “anti”
D “fully eclipsed
C “anti”
No torsional strain as the groups are staggered and CH3 groups
are par apart
A “gauche”
van der Waals forces between two CH3 groups are repulsive: the
electron clouds repel each other which accounts for 0.9
• Calculations reveal that
Kcal/mole at room
more energytemperature
compared to ~72% of the molecules of
anti conformer
butane are in the “anti” conformation, 28% are in “gauche”
conformation
B “partially eclipsed”
torsional strain and large van der waals repulsive forces
between the H and CH3 groups
D “fully eclipsed
Cyclopropane
• banana bonds
poor orbital overlap
HCH 115°
H
H
H
H H
H
H H
ring-flip
HA
HB
Chair conformation HB
flagpole hydrogens
1.8 A0
H
HH H
Boat conformation
H H
H H
Newman projection of the
boat conformation
Ha Ha He He
Ha He Ha He
He He He Ha Ha Ha
He Ha
Ha He Ha
He Ring flipping or
Ha Ha He He
inversion
Interconversions of Cyclohexane
H
1-1.15
boat
(4.2-6.3)
Twist boat
chair chair
• The energy difference between the chair, boat, and twist conformation of
cyclohexane are low enough to make their separation impossible at r.t. At room
temperature approx. 1 million introversions occur each other second.
• More than 99% of the molecules are estimated to be in chair conformation at any
given time
Monosubstituted cyclohexane
X
1,3-diaxial interaction
H H
X The black bonds are anti-
H
X periplanar
H H (only one pair shown)
H H
X H X
H H The black bonds are synclinal
(gauche)
H H (only one pair shown)
H H
X
CH3
CH3
CH3 CH3
1 gauche-butane interaction 4 gauche-butane interaction
0.9 kcal/mol 4 x 0.9 kcal/mol = 3.6 kcal/mol
Difference in stability between 3.6 - 0.9 = 2.7 kcal/mol
the conformational isomers
Diastereomeric, chiral and therefore resolvable
CH3 CH3
CH3 CH3
CH3
CH3 H3C
CH3
This has 3 gauche-butane
interactions
Enantiomeric, chiral and not resolvable
CH3
H3C
CH3 CH3
CH3
CH3
CH3
It is a resolavable molecule
2-gauche-butane interaction = 1.8 kcal/mol
CH3 CH3
CH3
CH3
CH3 Diastereomers, achiral
CH3
H3C
CH3
CH3 Both have plane of symmetry, achiral
OH
Disfavoured
OH
H H
t-butyl group
a locking group
Twist boat
Write preferred conformation for
Me OH
i-Pr
Me
OH Me
OH
favoured
Problem: Which of the following compounds are resolvable,
and which are non resolvable?Which are truly meso?
a) cis-1,2-cyclohexane diol; b) trans-1,2-cyclohexane diol;
c) cis-1,3-cyclohexane diol; d) trans-1,3-cyclohexane diol;
e) cis-1,4-cyclohexane diol; f) trans-1,4-cyclohexane diol.
Hint:
OH
OH
OH
OH OH
OH
OH
OH trans (resolvable)
Non resolvable (easily interconvertible by flipping)
OH
OH OH
HO
OH OH
cis (meso) trans (resolvable)
OH
OH
HO OH
HO
OH
achiral (absence of chirality center)
Rigid molecules from cyclohexane conformers
OH CO2 H O
O
HO
CO2 H
CO2 H CO H O O O
2
HO2 C
CO2 H
OH H H
OH O O
HO
OH
Me
Me H 11
1 13
17
H H
10
O
14
7
4
H H
H
H H
rigid mobile
H
3
Gauche-butane interactions
H C1 C2
4 2 C1 C3
C4 C3
1
G°(est) = 3(0.88) = 2.64 kcal/mol
Can you estimate the energy difference between the two methyl-decalins shown below?
Me Me
H H
Me
Me
H
H