Answers to Suggested Problems for Lecture 7: Diels-Alder Chemistry

1. The following reaction proceeds very slowly even at elevated temperature. Propose
how you could accelerate the reaction without decomposing the reactants and also
predict the major product.
The challenging aspect of this problem comes from the diene, which has an electron
withdrawing ketone at carbon 2 but an electron donating methylene at carbon 3. The
ketone has a bigger effect due to the large partial positive charge on the carbonyl
carbon. Therefore, this is an inverse electron demand Diels-Alder reaction, since a
strong electron withdrawing group is on the diene while an electron donating amine
group is on the dienophile. Adding AlCl 3 to the reaction should catalyze formation of the
product. The AlCl3 will act as a Lewis acid to coordinate a lone pair of electrons on the
ketone bonded to carbon 2 of the diene, increasing its reactivity with the dienophile.
Since the ketone dominates the partial charges on the diene, especially in the presence
of AlCl3, the major product should be the isomer where the ketone from the diene and
the amine from the dienophile are para to one another. (Note that the electron-donating
CH2 group at carbon 3 of the diene reinforces the regioselectivity, because it induces a
partial negative charge at C-4 of the diene.)

2. The following reaction gives an 8:1 preference for the diastereomeric product shown
below. What would you do to reverse the preference, i.e. to make the other diastereomer
the major product?

To get the other diastereomer as the major product, you should use the opposite
enantiomer of the auxiliary attached to the dienophile. This means that the configuration
at all three chiral centers should be inverted.

3. The following diene reacts with formaldehyde in a hetero-Diels-Alder reaction.

Propose a structure for the product.