Massachusetts Institute of Technology 5.13: Organic Chemistry II Fall 2003, S.

Tabacco

Optional Problem Set 8: Radicals

1. Please provide a detailed mechanism for the formation of each of the illustrated products.

Me Me H O

cat. t-BuOOt-Bu 100 C

Me Me Me

O Me Me

2. The decarbonylation of the two labeled pentenals shown below has been studied.
O

ROOR
H D D

D Me D H D

Dilute Solution Concentrated Solution

D O

1:1 1 : 1.5
D

ROOR
H

Me

Me

Dilute Solution Concentrated Solution

1:1 1 : 1.4

a) Please provide a mechanism for the formation of each of the four products. b) For each reaction, explain the effect of the concentration on the product distribution.

3. Please provide a mechanism for the illustrated reaction. Show the initiation and propagation steps.

O Cl S O Cl

ROOR HCl SO2

4. Please provide a mechanism for the formation of each product, and rationalize the predominant formation of A.
O Ph O Me

cat. t-BuOOt-Bu 120 C

Ph O

Me

Ph O

O Me

Me

major A

minor B

5. Please provide a mechanism for the illustrated transformation.

Br O OMe O H O OMe

n-Bu3SnH
AIBN,
OH

6. Identify A and B, and provide a mechanism for their formation.

N O O

CCl4 AIBN,

C6H4Cl3NS A

C4H7Cl B (3 vinyl H's in 1H NMR)

CO2

7. Please provide a mechanism for the illustrated transformation.

catalytic PhS

8. Please provide a mechanism for the illustrated transformation.

O Me O I

cat. AIBN, cat. HSnBu3

SnBu 3 Me