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• With multiple substituents, solid or dashed wedges are used to show positioning of
the groups or by showing the groups in either axial or equatorial positions
• An “UP” substituent could be axial or equatorial depending on how the ring is flipped
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Conformations of Disubstituted Cyclohexane's
Pattern 1, 2-(or) 1,4- 1,3- α – below the plane
β – above the plane
a – axial
cis- αα e,a e,e e – equatorial
ββ a,e a,a
+ =
+ =
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trans-1,2-Dimethylcyclohexane
• Trans conformation has both methyl groups equatorial and only a gauche butane
interaction between methyls (3.8 kJ/mol) and no 1,3-diaxial interactions
• The ring-flipped conformation has both methyl groups axial with four 1,3- diaxial
interactions
• Steric strain of 4 x 3.8 kJ/mol = 15.2 kJ/mol makes the diaxial conformation 11.4 kJ/mol
less favorable than the diequatorial conformation
Cis-1,2-susbstitution Trans-1,2-susbstitution
• Steric bulk almost and always prefers the equatorial conformation to avoid 1,3-diaxial
interactions
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Disubstituted Cyclohexane's
1,2-
1,3-
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Relationship Between Substituents in Dimethylcyclohexanes
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cis-1,3-Dimethylcyclohexane
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trans-1,3-Dimethylcyclohexane
• Both conformations have one axial and one equatorial methyl group, so they have the
same energy.
10
Large Interaction Energies can Preclude the Formation of
Chair Conformation
• Both chair conformations
require one of the bulky t-butyl
groups to occupy an axial
position.
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Why do We Study Conformations?
• Understanding conformations will help us understand stability of a molecule to predict
its reactivity
• Conformations can dictate reactivity.
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Conformations Influence Reactivity
• Both similar in energy so there is no significant preference for one over the other
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Conformations Influence Reactivity
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Conformations Influence Reactivity
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Bicyclic systems-Decalins
• Decalins are fused bicyclic compounds (10 carbon atoms) wherein the ring junctions
can be either cis- or trans.
• In cis-decalin hydrogen atoms at the bridgehead carbons are on the same face of the
rings
• In trans-decalin, the bridgehead hydrogens are on opposite faces
• The six-membered rings in cis- and trans-decalin assume chair conformations.
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cis- and trans-Decalins Are Not Conformers
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Bicyclic Compounds - Decalin
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Bicyclic Compounds - Decalin
cis-Decalin can flip as the new structure would also have one axial and one equatorial
bond
1 3 2
2 4 3 4
3
4 1
2
1
1 2
4 4
3 4 3
3
2
2
1
1 21
Polycyclic Ring Systems
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Chair Conformations are Ubiquitous In Nature
• The Haworth projection, although widely used, may give the impression of the ring
being flat.
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Chair Conformations are Ubiquitous In Nature
• The only difference in the two molecules is that the stereochemistry at the C1
carbon atom is different.
• Stereoisomeric molecules which differ in the configuration at only one stereogenic
center are called epimers.
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Epimers
• Epimers are stereoisomers that differ in the configuration at only one stereogenic
center.
• The carbon at which the stereochemistry differs is usually specified.
=>
25
Epimers and Anomers
• Anomers are actually epimers that differ in configuration at the acetal/hemiacetal
carbon.
• This carbon atom is also referred to as the “anomeric carbon”.
• Two anomers of D-glucose are shown below.
• The hydroxyl group on the anomeric (hemiacetal) carbon is down (axial) in the α
anomer and up (equatorial) in the β anomer.
• The hemiacetal carbon is called the anomeric carbon, easily identified as the only
carbon atom bonded to two oxygens. 26
Does the a-anomer Exist in Significant Amount?
❑ Despite what we saw for cyclohexane (huge preference for the equatorial
position), the corresponding a-D-glucose is present in significantly higher ratio.
36% 64%
❑ The axial substituent in this case seems to be more stabilized compared to the
corresponding cyclohexanol.
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11% 89%
Anomeric Effect
dipole moment
cancels out
s*C-X s*C-X
dipole moment enhanced
• Overlap between lone pair of
• Overlap NOT possible • Less dipole makes the
oxygen and antibonding
orbital of C-X possible - molecule more stable
Antiperiplanar arrangement is
essential
• As an extreme case, we can imagine complete donation of the lone pairs to give
the following resonance structure
Oxycarbenium
ion
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Stereoisomerism
• Isomers that have the same connectivity between atoms but different spatial
arrangement of their atoms are called stereoisomers.
• With rings and with C=C double bonds, cis-trans notation is used to distinguish
between stereoisomers
• Cis – Higher priority (CIP notation) groups are positioned on the SAME side of a
ring/double bond
• Trans – Higher priority (CIP notation) groups are positioned on OPPOSITE sides
of a ring/double bond
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Stereoisomerism
• Optical Isomerism
• Optical isomers, or enantiomers, are mirror images of one another that don’t
superimpose on each other.
• Their properties of chiral chemicals differ from each other only when they interact with
other chiral entities (such as plane polarized light).
31
An Interesting Side-Note About Enantiomers
32
An Interesting Side-Note About Enantiomers
33
Summary
• Axial and equatorial substituents position the orbitals appropriately, which helps in
• Cis-Decalin can flip and trans-decalin is locked cannot flip. Trans-decalin is 2.7
effect, which is accounted by antiperiplanar lone pair hypothesis as well as less dipole
stabilization
34