Chemistry 215 Second Examination June 5, 2013 (1.

5 hr; 120 points)

PRINTED Name ___________________________________

please print clearly please print clearly

Signature ________________________________ ID No. _______________________

Problem 1 2 3 4 5 total

Points 21 27 25 23 24 120

Score

GSI

Please read each question carefully and answer it completely and clearly. Precision in drawing is an important skill. Double-check any three-dimensional representations to ensure you are implying an unequivocal direction of bonding. Individual point values are given in the corner of each answer space. The exam has 7 pages including this cover page and the pKa table on the last page.

Name ___________________________________ Page 1 I. (21 points) Provide the reagents or structures as necessary to complete the following reactions or sequences of reactions. If more than one synthetic step is required, number them sequentially. You may use abbreviations for reagents (e.g. TsCl, NEt3), but not acronyms (e.g. mCPBA, PCCdraw the structure instead). If a mixture of stereoisomers is formed draw only one isomer.

Name ___________________________________ Page 2 II. (27 points) A. Predict the Keq for each of the following combinations below. (6 points)

B) It is challenging to make peptides using acid chlorides of amino acids because you obtain the unwanted side reaction below, where two amino acid chlorides react with each other. Provide a mechanism for the reaction below. You may use B: as a generic base.

Name ___________________________________ Page 3 III. (25 points) A. a) Peptide 1 can be synthesized from two amino acids. In the boxes below provide the two amino acid starting materials.

b) The reaction above will produce more than 1 peptide product. Circle the functional groups in your starting amino acids that would need to be protected to get peptide 1 as the sole peptide product. (2 points) B) Aspartame is an artificial sweetener that is found in diet sodas and can be synthesized from two amino acids. One possible synthesis is shown below. It relies on an enzyme catalyzed selective amide bond formation. Fill in the missing amino acid starting materials and the reagents needed to complete the synthesis.

C) Draw the structure of ethyl 4,4-dimethoxybutanoate.

Name ___________________________________ Page 4 IV. (23 points) a) Draw the best resonance structure of the conjugate base of 1 in the box below.

b) The pKa values for these four molecules below are 31, 23, 11.4, and 7.1. Predict which pKa goes with which molecule in the boxes below.

c) When 1 is treated with base and deuterated water the acidic hydrogen on the molecule are replaced with deuterium. Draw a mechanism for this transformation. You may use B- for a base.

Name ___________________________________ Page 5 V. (24 points) Provide the structures as necessary to complete the following reactions or sequences of reactions. If more than one synthetic step is required, number them sequentially. If a mixture of stereoisomers is formed draw only one isomer.