M. Movassaghi Problem Set III Chemistry 5.

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Due in class: Monday, Mar. 12th, 2007 at 12:05 pm. Monday 3.5.2007

In your answers, show arrow pushing and where appropriate identify 4. Provide a detailed mechanism for the following. Specify the
initiation and propagation steps. initiation and propagation steps. What is the by-product X?

H3C
1. Provide a detailed mechanism for the following: H AIBN
O OEt + CHCl3 + X
H3C Δ
t-Bu O Cl Cl
H3C CH3 O t-Bu N
O
N CH2 (racemic, mixture of
+ diastereomers)
EtO Δ

H3C CH3
5. Provide a mechanism for the formation of each of the four products.
(mixture of diastereomers) Explain the effect of concentration on the product ratios.

2. Provide a detailed mechanism for the following. Explain the O t-Bu O

D D
O t-Bu
stereochemical outcome including the double bond geometry? (a) + H
H Δ CH3
D D D D
dilute reaction mixtures: 1 : 1
H3C H concentrated reaction mixtures: 1 : 1.5
AIBN
CH3
CH3
CH3 n-Bu3SnH D O t-Bu O D
H3C O t-Bu
Δ (b) H +
H3C Br CH3 Δ D CH3 CH3

(racemic) (racemic, mixture of dilute reaction mixtures: 1 : 1

diastereomers) concentrated reaction mixtures: 1 : 1.4

3. Provide a detailed mechanism for the following: 6. Provide a detialed mechanism for the following:

CH3
AIBN O
O O O CH3 AIBN O O
n-Bu3SnH n-Bu3SnH O
O I H N CH3
I
Δ N Δ

Ph

1/1