Conformational Analysis Newman Projections Ring Strain Cyclohexane Conformations

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Conformational Analysis Newman Projections Ring Strain Cyclohexane Conformations

Conformational Analysis Newman Projections Ring Strain Cyclohexane Conformations

Views of Ethane

Views of Ethane

The Newman Projection

The Newman Projection

Rotational Conformations of Ethane

Rotational Conformations of Ethane

Definitions • Conformations - Different spatial arrangments that a molecule can adopt due to

Definitions • Conformations - Different spatial arrangments that a molecule can adopt due to rotation about sigma bonds. • Staggered - A low energy conformation where the bonds on adjacent atoms bisect each other (60 o dihedral angle), maximizing the separation. • Eclipsed - A high energy conformation where the bonds on adjacent atoms are aligned with each other (0 o dihedral angle).

o 60 Rotation Causes Torsional or Eclipsing Strain

o 60 Rotation Causes Torsional or Eclipsing Strain

Types of Strain • Steric - Destabilization due to the repulsion between the electron

Types of Strain • Steric - Destabilization due to the repulsion between the electron clouds of atoms or groups. Groups try to occupy some common space. • Torsional - Destabilization due to the repulsion between pairs of bonds caused by the electrostatic repulsion of the electrons in the bonds. Groups are eclipsed. • Angle - Destabilisation due to distortion of a bond angle from it's optimum value caused by the electrostatic repulsion of the electrons in the bonds. e. g. cyclopropane

Definitions • Anti - Description given to two substitutents attached to adjacent atoms when

Definitions • Anti - Description given to two substitutents attached to adjacent atoms when their bonds are at 180 o with respect to each other. • Syn - Description given to two substitutents attached to adjacent atoms when their bonds are at 0 o with respect to each other. • Gauche - Description given to two substitutents attached to adjacent atoms when their bonds are at 60 o with respect to each other.

Propane Conformations: Larger Barrier to Rotation (link)

Propane Conformations: Larger Barrier to Rotation (link)

Butane Conformations (C 2 -C 3)

Butane Conformations (C 2 -C 3)

Gauche Interaction in Butane

Gauche Interaction in Butane

2 Different Eclipsed Conformations

2 Different Eclipsed Conformations

Strain Energy can be Quantified

Strain Energy can be Quantified

Butane has Steric and Torsional Strain When Eclipsed

Butane has Steric and Torsional Strain When Eclipsed

PE Diagram for Butane (link)

PE Diagram for Butane (link)

1 -Chloropropane

1 -Chloropropane

Saturated Cyclic Compounds

Saturated Cyclic Compounds

Cyclopropane Angle and Torsional Strain

Cyclopropane Angle and Torsional Strain

Electron Density Map

Electron Density Map

All Dihedral Angles = 0 o

All Dihedral Angles = 0 o

Cyclobutane is not Planar

Cyclobutane is not Planar

Cyclopentane

Cyclopentane

Cyclohexane

Cyclohexane

Chair Conformation link to active site

Chair Conformation link to active site

Boat Conformation

Boat Conformation

How to Draw a Chair Conformation all opposite bonds are parrallel

How to Draw a Chair Conformation all opposite bonds are parrallel

Axial bonds and Equatorial bonds

Axial bonds and Equatorial bonds

Rings can Flip from one Chair Conformation to Another

Rings can Flip from one Chair Conformation to Another

Flipping Chair Conformations • • All axial bonds become equatorial All equatorial bonds become

Flipping Chair Conformations • • All axial bonds become equatorial All equatorial bonds become axial All “up” bonds stay up All “down” bonds stay down

Axial-up becomes Equatorial-up

Axial-up becomes Equatorial-up

Equatorial Conformation is Preferred (link)

Equatorial Conformation is Preferred (link)

Axial Methyl group is Gauche to C 3 in the ring

Axial Methyl group is Gauche to C 3 in the ring

Gauche Interactions are Flagged by Parallel H’s 1, 3 -Diaxial Interactions

Gauche Interactions are Flagged by Parallel H’s 1, 3 -Diaxial Interactions

Equatorial Methyl Group is Anti to C 3 in the ring

Equatorial Methyl Group is Anti to C 3 in the ring

cis 1, 3 -Dimethylcyclohexane

cis 1, 3 -Dimethylcyclohexane

trans 1, 3 -Dimethylcyclohexane

trans 1, 3 -Dimethylcyclohexane

cis 1 -Chloro-4 -t-butylcyclohexane

cis 1 -Chloro-4 -t-butylcyclohexane