CHEM 5000 Homework 1

1. Draw the most stable conformation of the following molecule.

The most stable conformation was shown below:

The above one is Newman projection of the most stable conformation. The lone pair of oxygen
would interact with the antibonding orbital of C-O bond, which could stabilize the conformation.
This interaction exists at both oxygen atom.

There is another conformation that possess these interactions as well. However, the
latter conformation have significant steric hindrance that make the conformation less
stable.

2. Predict Keq (>1 or <1) for the following equilibrium and rationalize
your prediction

a) Keq > 1, anomeric effect

b) Keq < 1, 1) -F has smaller A value than methoxy group

2) stronger anomeric effect for σ*C-F

c) K1 >1, K2 < 1, anomeric effect (different amount of hyperconjugation)

3. For the molecule below, please give the most stable conformation.
When treated it with nucleophile under proper nucleophilic substitution
condition, which bromide would be the most likely to be substituted?
Please rationalize your answer.

The above structure is the most stable conformation of given molecule.

In the conformation, the antibonding orbital of the axial C-Br bond would interact
with the axial lone pair electron of the oxygen. This interaction would make the
conformation more stable but weaken the C-Br bond. Thus, the axial Br would be
easier to be substituted.

4. Carboxamides have rotational barriers on the order of 20kcal/mol for

the process:

Develop a structural explanation for the barrier in MO terminology.

Amides prefer planar geometry because of the resonance stabilization. The barrier
to rotation is associated with the disruption of this resonance. In MO terminology,
the orbital with the C=O "∗ orbital provides a stabilized delocalized orbital. The
nonplanar form leads to isolation of the nitrogen unshared pair from the C=O
system