Dr. rer.nat.

Angelina Hormaza, Universidad Nacional de Colombia -Sede Medelln

Universidad Nacional de Colombia Sede - Medelln

Escuela de Qumica Maestra en Ciencias-Qumica
ORGANIC CHEMISTRY ADVANCED

Workshop about Pericyclic Reactions

1. Suggest a mechanism for the following transformations; they include more than one-step to
reach the final product.
CH3
a.

200 C

..
N

N
..

CH3

C2H5
H3CO

OCH3
H3CO2
+ CH3O2CC CCO2CH3
H3CO2

H3CO

OCH3 O

2. Give the product structure, including the expected stereochemistry for each of the following
reactions.

a.

C C O

b.

c.

+ CH3O2CC CCO2CH3
O
H3C

d.

+
H

CH CH2
O

3. Using the frontier orbital theory showing that the reaction of pentadienyl cation to the
cyclopentyl cation is permitted by conrotatory movement.
4. Based on the frontier orbital theory, explain if the following cycloaddition [4 +2] reaction is
thermally allowed.

Dr. rer.nat. Angelina Hormaza, Universidad Nacional de Colombia -Sede Medelln

5. Suggest a mechanism for the following process; they include more than one step to reach
the final product.
CH3

CH3

a.

80 C

OCH3
b.

+ H2C CCH2Br

Ag+O2CCF3
Na2CO3

H+
H2O
O

6. Write the structure product, including the expected stereochemistry for the following
reactions. In any case is probable that the substrate does not show any kind of pericyclic
reaction.
CH3O2CNH
a.

H
C C

H2C CH CO2CH3

CH CH2
O
CH3

b. CH2

CHCH CH2 +
H3C
O

PhS
c.

OCH3
C C

H2C CH C CH3

EtAlCl2

I
n-BuLi

d.
I
e.

f.

Base

N
PhH2C

7.

CH2CO2Et

Using frontier orbital theory show that the reaction of pentadienyl anion to the
cyclopentadienyl is thermally allowed by disrotatory movement.

Dr. rer.nat. Angelina Hormaza, Universidad Nacional de Colombia -Sede Medelln

8.

Based on the frontier orbital theory, stablish if the following addition reaction [6+2] is
thermally allowed. Explain briefly.
+

9. The following reactions will be allowed under the conservation of orbital symmetry? Explain
briefly what kind of changes occurred.
S

S
S
a.

CN
CN

(CN)2C C(CN)2

S
CN CN
H
b.

CH3

CH3
C C
C C

CH3
H

H
C C

CH2OSi(CH3)3

C C

CH3CH2
H

OSi(CH3)3

10. Write the product structure, including the expected stereochemistry for each of the following
reactions.

a.
OH
CH CH2
O

b.

Ph

K OC(CH3)3

CH 3

OSiR3
calor

c.
CH O

CH2

d.

(C2H5)3N

H
CH2C

Cl

O
O
hv

e.
CH3
calor

f.

hv

Dr. rer.nat. Angelina Hormaza, Universidad Nacional de Colombia -Sede Medelln

11. Using the orbital correlation diagram shows that the reaction of 1,3,5-hexatriene
electrocyclization is allowed for a disrotatory movement and prohibited for a conrotatory
movement
12. Write the product structure, including the expected stereochemistry for each of the following
reactions and identify the type of transformations.
O
a).

H3PO4

13.
Using the analysis of frontier orbital theory shows that the 1,7-sigmatropic shift of hydrogen
is allowed through an antarafacial interaction. For this, consider the 1,3,5-heptatriene.
14.
It was found that the electrocyclization of 1,3,5-hexatriene is allowed through an
conrotatory movement under photocatalytic conditions. Offers an explanation of this fact.

I hoffe, you enjoy this workshop !!!

Prepared by: Dr. rer. nat. Angelina Hormaza

Update: Medelln, May / 2016