These problems are taken from previous exams given by Professor Baranger. 1.

(20 points) Draw the major products for the following reactions. Be careful to indicate stereochemistry and to draw all stereoisomers formed.

(a)

1) O3, CH2Cl2 2) H2O2,

O OH

(c) H2 Pd/C (d) 1) OsO4, THF 2) H2O, Na 2SO3

2. (25 points) Addition of HBr to 2-methylpropene under two different sets of conditions is shown below.

HBr

Br

HBr, ROOR, h!

Br

(a) Draw the mechanism with arrows for the first reaction with HBr above. (b) Draw the mechanism with arrows for the reaction with HBr and ROOR. (c) Based on the mechanisms you drew in part a, explain the differences in regioselectivity. For each reaction, explain why the intermediates that lead to the formation of the correct regioisomer are more stable.

3. (25 points) Reaction of alkene with BH3 gives the alcohol drawn below, while reaction with a comparable alkyne does not give an alcohol, but rather an aldehyde.

1) BH3, THF 2) H2O2, Na+ OH 1) HBR2, THF 2) H2O2 , Na+ OH R = cyclohexyl

O

OH

a) Draw the mechanism with arrows for the addition of BH3 to the alkene. You do not need to draw the mechanism of the step involving H2O2. b) Draw the mechanism with arrows for the addition of BH3 to the alkyne. Again, you do not need to draw the mechanism of the step involving H2O2, but you must show why an aldehyde is formed instead of an alcohol. c) Identify and draw the HOMO and LUMO that react for the first step of each reaction. 4. (16 points) Outline a synthetic route for the following molecules from the starting material given. Make sure to design the synthesis that will give the highest yield of the correct product.

(a)

Br Br

Br Br

and

from

(b)

and
H

from

4. (28 points) Give the major product(s) of the following reactions. Be careful to indicate stereochemistry and to draw all of the stereoisomers that are formed.

(a)

1) OsO4, CH2Cl2 2) H2 O2 ,
O OH

(c)

CH3 H

CH 3 Br

CH3CH2OH

(d) +
F3C

O OOH

(e) + Br2

h!

(f)

Br2

CCl 4

(g)

1) BH3, THF 2) H2O2, Na+ OH

5. (20 points) (a) Label all stereocenters found in the products you drew in question 1 as (R) or (S). (b) For reactions in problem 1 that form more than one stereoisomer, identify whether they are enantiomers or diastereomers of each other. (c) Choose any two reactions from part 1 and identify and draw the HOMO and LUMO that react. If the reaction has more than one step, you may draw the HOMO and LUMO for any step of the reaction. 7. (20 points) Which reaction in each of the following pairs would proceed at a faster rate? Explain your choice in a few sentences.

(a)
I

Na+ NH2

NH3

NH2

NaI

or
I

NH3

NH2

HI

(b)

H2 O

OH

HI

or
I

H2 O

OH

HI

(d) I +

Na+ OCH2 CH3

CH3CH2OH

or I +

Na+ OCH2 CH3

CH3CH2OH

8. (21 points) (a) Draw Newman projections for the staggered and eclipsed conformations of (S)-2,3-dimethylhexane looking down the 3,4 bond. (b) Draw and energy versus dihedral angle graph for rotation around the 3,4 bond of (S)2,3-dimethylhexane. and an energy diagram.

9. (30 points) SN1 and E1 reaction compete with each other. Using 2-methyl-2iodobutane, shown below, answer the following questions.

(a) Write an example of an SN1 reaction using 2-methyl-2-iodobutane as a substrate. Use conditions such that a minor amount of E1 product will be formed and draw this product. (b) Write the mechanism with arrows for the SN1 reaction. (c) Write the mechanism with arrows for the E1 reaction. (d) Write the rate equation for each reaction. (e) Draw the SN1 and E1 reactions on the same reaction coordinate diagram. (f) Use the reaction coordinate diagrams you drew in part (e) and the Hammond postulate to explain why it is difficult to perform reactions that produce products only from SN1 reactions or only from E1 reactions. 10. (25 points) Consider the two reactions below:
O

Na+ OH H2 O

H3 O+ H2 O

(a) Draw the products of the two reactions. (b) Draw the mechanism with arrows for each reaction. (c) If the product of the reaction with Na+ OH has a specific rotation of +20, what will be the specific rotation of the product from the reaction with H3O+? (d) What would be the specific rotation of a mixture that was composed of 20% of the product from reaction with Na+OH and 80% of the product from reaction with H3O+.