Problem Set 1

Chem 3B, Spring 2016

MaryAnn Robak

Note: Some of these problems are used with permission from: Pedersen, S. F. Chemistry 3B Midterm and Final
Examinations; 2nd ed.; Hayden McNeil: Plymouth, MI, 2013.

1. A. Draw a mechanism that accounts for all six of the brominated products shown. Note: You do not have to
show the mechanism for how Br2 is generated from NBS, just draw the balanced reaction step.

B. Consider the resonance stabilized intermediate that leads to products A and B above. Why is there NOT
a second pair of products arising from the other resonance contributor of this intermediate?

Page 1 of 10
2. Predict all of the possible organic product(s) from the following reactions. Where relevant, show all
stereoisomers. Pay particular attention to any information given in the product boxes. Each redundant or
wrong answer within a box cancels out a correct answer.

Page 2 of 10
3. Predict all of the possible organic product(s) from the following reactions. Where relevant, show all
stereoisomers. Pay particular attention to any information given in the product boxes. Each redundant or
wrong answer within a box cancels out a correct answer.

O
hv
+ N Br
O
O
+ N H

O
hv
N Br
+
O
O
+ N H

monobrominated products only O

O
hv
+ N Br
O
Ph O
+ N H

OH
hv
+ N Br
O
O
+ N H

Page 3 of 10
4. A. Complete the curved arrow mechanism below (add any missing structures and all curved arrows).
CH3
O
Br Br Br Br
+ + HBr
CH3OH O
CH3

H CH3
Br O
Br

Br
H
O
CH3

B. The addition of Br2 to an isolated alkene proceeds through a cyclic bromonium ion intermediate.
Draw a mechanism illustrating this statement, using cyclohexene as the starting material.

C. In 5 words or less, what effect does the cyclic intermediate in part B have on the controlling the
stereochemical outcome of that reaction?

D. Addition of Br2 to a conjugated diene does not involve a cyclic bromonium ion intermediate (as
illustrated in part A). Propose a reason for this mechanistic difference.

E. The scheme in part A does not include stereochemistry. Predict the structures of all products that could
be formed by the reaction in part A, including stereochemistry.

F. Explain why the structure below is NOT one of the products formed under the reaction conditions in
part A. (5 words or less plus a picture of the relevant intermediate structure)

Page 4 of 10
5. Draw a curved arrow mechanism for each of the reactions shown below. Your mechanism must account for
all product(s) shown. (Note: For some of these reactions, there may be other possible products that are not
shown. You only need to explain the product(s) pictured in the scheme)

Page 5 of 10
6. Draw a curved arrow mechanism for each of the reactions shown below. Your mechanism must account for
all product(s) shown. (Note: For some of these reactions, there may be other possible products that are not
shown. You only need to explain the product(s) pictured in the scheme)

Page 6 of 10
7. Draw a curved arrow mechanism for each of the reactions shown below. Your mechanism must account for
all product(s) shown. (Note: For some of these reactions, there may be other possible products that are not
shown. You only need to explain the product(s) pictured in the scheme)
1.
SH O K S S
+ + + KBr
OH
2. CH3Br

OH HCl + H2 O

Cl

OPP + HOPP
farnesyl pyrophosphate
(PP = pyrophosphate) bisabolene (a sesquiterpene)

Page 7 of 10
8. Predict all of the possible organic product(s) from the following reactions. Where relevant, show all
stereoisomers. Pay particular attention to any information given in the product boxes. Each redundant or
wrong answer within a box cancels out a correct answer.

Page 8 of 10
9. Predict all of the possible organic product(s) from the following reactions. Where relevant, show all
stereoisomers. Pay particular attention to any information given in the product boxes. Each redundant or
wrong answer within a box cancels out a correct answer.

Page 9 of 10
10. Predict all of the possible organic product(s) from the following reactions. Where relevant, show all
stereoisomers. Pay particular attention to any information given in the product boxes. Each redundant or
wrong answer within a box cancels out a correct answer.

1. 2 Li
Cl
2. O

3. H3O

3 products including stereoisomers

1. HBr
OH 2. Mg

3. D2O

1. BuLi

2.
O

3. H2O workup

All products with molecular formula C14H20O including stereoisomers

Page 10 of 10