Organic Chemistry

(Dana P.) #1
Problems 127


  1. Chorismate mutase is an enzyme that promotes a pericyclic reaction by forcing the substrate to assume the conformation needed
    for the reaction. The product of the pericyclic reaction is prephenate, which is subsequently converted into the amino acids
    phenylalanine and tyrosine. What kind of a pericyclic reaction does chorismate mutase catalyze?

  2. Account for the difference in the products of the following reactions:

  3. Show how norbornane could be prepared from cyclopentadiene.

  4. Give the product formed when each of the following compounds undergoes an electrocyclic reaction
    a. under thermal conditions
    b. under photochemical conditions









  5. Give the product of each of the following reactions:


a. c. e.

b. d.


  1. Which is the product of the following [1,3] sigmatropic rearrangement, A or B?

  2. Dewar benzene is a highly strained isomer of benzene. In spite of its thermodynamic instability, it is very stable kinetically. It will
    rearrange to benzene, but only if heated to a very high temperature. Why is it kinetically stable?



Dewar benzene

very slow


OCCH 3

O

H
H
D

OCCH 3

O

H
D
H

D
H

H

H 3 CCO

O

AB


O

CH 3

CH 3 ∆


O

CH 3


OH
h

CH 3
H 3 C

CH 3

CH 3

norbornane

H

H

H

H

chorismate

COO−

HO H

H

OCCOO−

chorismate mutase

prephenate

CH 2

−OOC

HO H

CH 2 CCOO−

O
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