You are on page 1of 5

CHEM

302

Practice Problems --- Pericyclic Reactions 1. Which Diels-Alder reaction would you expect to proceed at the highest rate? What would you expect the regiochemistry and stereochemistry of the product to be? a)
O H O H O H O H

b)
OMe O Me


OMe O Me

c)
OMe O H


OMe O H

2. In the first total synthesis of a steroid, Woodward started with a Diels-Alder reaction. Explain why the following Diels-Alder reaction would form the first product and not the second.
O Me MeO O MeO O O Me not O OMe

3. Provide the mechanism of the following reaction. Would you perform the transformation under thermal or photochemical conditions? Justify your answer.
O

Me

CHEM 302 4. The photolysis of a mixture of cis and trans cyclododecaen-7-yne gave two products. Suggest which isomer gave predominantly which product and explain your choice.

H H +

hv

H H 5. The following alcohol remains stable until oxidation to the corresponding ketone. Cyclization is observed immediately. Explain this change in reactivity, provide the cyclization mechanism and reason for the stereochemistry.

6. Although it gets used in synthesis all the time, cyclopentadiene is a somewhat unstable species. Upon standing at room temperature for extended periods of time, it slowly undergoes a dimerization. In fact, when purchased from a chemical company like Aldrich, it is sold as the dimer which is "cracked" by heating at high temperature (>150 C) to provide the monomeric species we use everyday. Consider possible cycloaddition pathways ([2+2], [4+2] and [4+4]) and decide what the most likely product would be. 7. Under what conditions, thermal or photochemical, would you expect the following reaction to occur?
Me Me Me Me
2 ?

CHEM 302 8. State whether the following reaction is conrotatory or disrotatory. Under what conditions (thermal or photochemical) would you carry it out?

9. Predict the product(s) under thermal and photochemical conditions.


Me ! and h" H Me

10. Dewar benzene (shown below left) is an interesting molecule. It is stable at room temperature, even though its isomerization to benzene by an electrocyclic opening of either cyclobutene ring should be exothermic by 79 kcal/mol (approximately the strength of a carbon-carbon bond). Using your knowledge of the Woodward Hoffman rules, explain why Dewar benzene does not easily isomerize to benzene. Assuming you could excite an electron on the -bond, would you expect it to be stable to light?
H H

11. Which pericyclic reaction is responsible for the following transformation? Under what conditions? Explain the resulting stereochemistry.

CHEM 302 12. Predict the stereochemistry of the product under the given conditions.
hv

a)

H H

13. Predict the product(s) of the following reaction.

b)

14. Explain the selectivity observed when the nine-membered ring was subjected to either thermal or photochemical conditions.

15. Explain the difference in reactivity in the following systems.


CH3 R H 3C H CH3 R

h!

H 3C

CH3 R H 3C H

CH3 R

h!

H 3C

CHEM 302 16. Provide a mechanism for the following reactions and identify the pericyclic process(es). a)

b)


H H !

OH 17. Draw a reasonable 2-step mechanism for the following (reaction under thermal conditions). OH

c)

18. Predict the product.


OH O O O Ph
CH3C(OCH3)3 H+, 150 C

19. Predict the product, including stereochemistry.


O !

20. Identify the pericyclic process(es) involved in the following transformation. Provide a mechanism.
Me O H ! MeO H MeO H H Me O

You might also like