Chemistry 3OA3

Assignment 1 ANSWER KEY

Question 1. Propose syntheses for the following compounds.

(a)
from
O

Answer:
O
1. ClMg

, ether

2. H3O+
H2SO4, heat
or 1. TsCl, pyridine
2. Et3N

HO
1.

heat

+
O

, NaNH2, NH3 (l)

O
O

2. H2, Lindlar's catalyst

maleic anhydride
(buy it)

(b)

OHC
from

Answer:
O
+

heat

O
H

1. LDA, THF, -78C

2.

benzaldehyde
(buy it)

O
H

OHC
O

OH

NaBH4
OH

H+

OH

O
O

heat

O
(c)

CO2Et
from

CHO
NH2

Answer:
CO2Et
NO2

O-

H2

1. nBuLi
2.

Pd/C
CO2Et
O
H

NO2

NO2

O
NH2

(d)

CO2H

from

Answer:
O

O
AlCl3

Ac2O

CO2H
CO2H

1. O3

1. NaBH4

2. H2O2

2. conc. H2SO4

O
CO2H
O

1. O3
2. H2O2
O
O

O
conc.

OH

H2SO4

1.

2. H3O+

MgBr
Mg, ether

Br2
FeBr3

O
Br

Question 2. Propose a mechanism for the following reaction. Show all steps for full
marks.

CO2Me

1. mix

(Et)2NLi

2.

CO2Me

H3O+

N
CO2Me
CO2Me

Answer:

N
O

OMe

OMe

OMe

OMe

MeO
H3O+

TM

CO2Me

Question 3. The sex attractant of a female beetle that bores into the ponderosa pine
has an unusual bicyclic structure. The compound, called brevicomin, is shown
below. Brevicomin was synthesized by the following sequence of reactions.
Provide the structures for the intermediates and products indicated by the letters.
O

CH3CH2ONa
OEt

H3C

1. H+ / H2O

Br-(CH2)3-Br

OH

HO

(C6H5)3P

TsOH

2. heat

1 equivalent

ethanol

CO3H

Cl
H
butyl lithium

benzene

toluene

diethylether

benzene
O

H3O+

I
(not isolated)

OH

Answer:

brevicomin

O
H3C

H3C

OEt

H3C

OEt

_
Na

Br

Br
E

D
O

F
O

H3C

H3C

+PPh

Br

Br

PPh3

G
O

H3C

I
O

OH

OH