1. Choose the answer that has the following compounds located correctly in the separation scheme.

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1 CE 322 Final Exam Spring 2010 Form Choose the answer that has the following compounds located correctly in the separation scheme. A. toluene is in (X); phenylacetic acid is in (Y); benzylamine is in (Z). B. toluene is in (Y); phenylacetic acid is in (Y); benzylamine is in (Z). C. toluene is in (Y); phenylacetic acid is in (X); benzylamine is in (Z). D. toluene is in (Z); phenylacetic acid is in (Y); benzylamine is in (X). E. toluene is in (Z); phenylacetic acid is in (X); benzylamine is in (Y). 2. Which of the following compounds is anti aromatic? 3. One step in glycolysis involves the oxidation of the aldehyde, glyceraldehyde 3 phosphate, to a carboxylic acid derivative. Which of the following compounds serves as the oxidant in this reaction? A. ATP B. ADP C. NAD + D. NAD E. Acetyl coenzyme A 4. Which of the following labeled hydrogen atoms would be the most acidic?

2 CE 322 Final Exam Spring 2010 Form A student was asked to draw a curved arrow mechanism for the acid catalyzed isomerization of glucose to fructose. O O O O O O 2 O glucose fructose Which of the following structures is the best representation of a key intermediate in the isomerization reaction? O O O O O O 6. In the opening steps of the biosynthetic path to cholesterol synthesis acetyl Coenzyme A reacts with its own enolate in a reaction similar to a Claisen condensation. What is the final Claisen like product of this reaction sequence?

3 CE 322 Final Exam Spring 2010 Form Which of the following molecular orbitals best represents the OMO of the pentadienyl cation? 8. Choose the major product of the following reaction. 9. Predict the major product of the following organometallic reaction.

4 CE 322 Final Exam Spring 2010 Form Predict the major product of the following reaction sequence. 11. Solanapyrone is a fungal inhibitor of mammalian DNA polymerase. It is notable because it is made by the fungi by an enzyme catalyzed Diels Alder reaction as shown below. The enzyme catalyzes the intramolecular Diels Alder reaction of prosolanopyrone to solanapyrone. Identify the structure of prosolanopyrone. 12. Identify reagent X in the following reaction.

5 CE 322 Final Exam Spring 2010 Form The sesquiterpene bergamotene is a component of valerian root oil. The biosynthetic pathway from farnesyl pyrophosphate to bergamotene is shown below. Identify the structure of bergamotene. 14. Five possible syntheses of the amine below are shown. Which one would not work?

6 CE 322 Final Exam Spring 2010 Form Identify the major product of the following reaction sequence. 16. When 1 phenylbutadiene reacts with Br the same major product is found at both high and low temperatures. Identify this major product. 17. Which of the following phenols is the most acidic? O O O O O O C 3 NO 2 O NO 2 3 C A B C D E

7 CE 322 Final Exam Spring 2010 Form Brachyose is a disaccharide of glucose and is found in beer. Deduce the structure of brachyose from the following information. i. Brachyose is hydrolyzed by glucose enzymes, but not by glucose enzymes. ii. Methylation of brachyose followed by hydrolysis yields the two derivatives shown below. Brachyose C 3 I + NEt 3 2 O 3 CO CO OC 3 OC 3 O C 2 OC CO CO OC 3 OC 3 O C 2 O Identify the structure of Brachyose Answers to the following short answer questions should be given at the indicated space on your answer sheet. Points will be given as indicated for each question. 19. (a) Identify the following sugar by circling the appropriate letter A through from the above figure. (b) Designate the configuration of the anomeric carbon atom by circling or. (6 pts)

8 CE 322 Final Exam Spring 2010 Form Give the major product of the following reaction. (6 pts) 21. Give the major product of the following reaction. (6 pts) 22. The following two tosylates, A and B, were treated with base. The cis isomer A gave a bicyclic (2 rings) compound with formula C 6 10 O. The trans isomer B gave an acyclic (0 rings) compound of the same formula. Use your knowledge of organic mechanisms as a guide and predict the two products. (12 pts) Note: You do not need to show the mechanisms just the two products. 23. The compound valproic acid is an anticonvulsant and mood stabilizing drug. It can be prepared via the following reaction sequence. What is the structure of valproic acid? (8 pts)

9 CE 322 Final Exam Spring 2010 Form Give a synthesis of the compound shown below starting with benzene. Your product should be free of the para isomer. (8pts) 25. The drug ecstasy or 3,4 methylenedioxymethamphetamine is an illicit drug. It can be made from safrole, a compound that can be isolated from the roots of a sassafras tree. Give a sequence of reactions that could be used to convert safrole to ecstasy. (8 pts) 26. Celestolide is perfume component that has a musk like odor. It can be prepared by the following reaction sequence. Identify compounds A, B and C. int: Celestolide is a bicyclic compound with a molecular formula C O. (12 pts) O O Zn(g) Cl Cl C 3 A B C AlCl 3 Cl AlCl 3 C O bicyclic

10 CE 322 Final Exam Spring 2010 Form The terpene sabinene can be isolated from the Norway spruce. It is one of the compounds that contributes to the spiciness of black pepper. Give a curved arrow mechanism that shows the bond breaking and bond making along the biosynthetic pathway of the formation of sabinene from geranyl pyrophosphate. (12 pts) 28. Norbisabolide is a compound isolated from the root bark of the Indian Atlantia tree. Give a synthesis of norbisabolide from compounds containing 4 carbons or less. (12 pts) int: You may wish to form your lactone in the last step.