Cycloadditions Solutions 2013 2

HETEROCYCLIC CHEMISTRY Part 3
Modules 06710-12-14
DIPOLAR CYCLOADDITION CHEMISTRY

1.
Identify the dipole structures from the reagents given

1. NaOCl
2. base
NOH
NOH
_
+ O
N
_
+ O
N
Et3N
Cl
1. NH2OH
NaOAc
OCH3
Me
2. NCS
3. Et3N
_
O + Me
N
Me-NH-OH
Me
Ph-NH-OH
_
Ph + O
N
_
+ O
N
N
H
g
Ph
Ph
NH
_
+ O
N
CH3O
OH
Et3N
Ph
+
N
_
N Ph
Cl
page 1
CO2Et
NH
Modules 06710-12-14
Et3N
_
N CO2Et
+
N
Cl
Cl
Cl
O
N
H
H2N
H
N
1. POCl3
2. Et3N
+
N
Ph
CH3
_
N CH3
Et
NH
N
NH
O
+
Et
H
N
+
N_
heat
OMe
MeO
MeO
Me
Me
O
NH NH Me
Me
Ph
Me
Ph
+ _
N N N
2. NaN3
_
N
N+
N
1. NaNO2, HCl
O
O
2.
N
_
N
+
Me
1. NaNO2, HCl
NH2
NH2
heat
Et
2. NaN3
Name the class of dipole in the following reactions and give their
structure
+ _
N N
Ph N N N
Ph
N
Ph
Ph
Ph
AZIDE
Ph
page 2

Me
N+ _
O
Me N
NITRONE
Me
_
+
N O
Ph
Me
Me
Me
O
Modules 06710-12-14
Me
O
N
NITRILE OXIDE
Me
Ph
3.
Identify the dipolarophile in the following reactions and give their

structure
Ph N N N
Me
Ph
Ph
N N
N
Me
Ph
O
Me
O N C Me
N O
O
Me
Me
Me
N O Me
O N C Me
Me
H
O
4.
Identify the cycloadducts from the following reactants showing the

correct stereochemistry where appropriate.
Ph
+
Ph
Ph
N
Ph
Ph
Ph
page 3

b
Me
Ph
Modules 06710-12-14
Me
Me
N
Ph
Me
c
O
Ph
N
Ph
H
O
Ph
CO2Et
+
Ph
CO2Et
Ph
Ph
Ph
Me
EtO2C
Me
N
N
Me
Ph
EtO2C
Me
CO2Et
N
Ph
CO2Et
O
Ph
Me
N
Me
Ph
O
Me
Ph
Me
h
O
+ Me
N
Me
Me
Me
Me
Me
N
Me
H
Me
page 4
Modules 06710-12-14
H
Me
Me
85 C
OMe
N
+
O
OMe
H
O
+ Me
N
Ph
5.
exo attack
Ph
N
N
N tBu
Ph
_
t
O + Bu
N
Ph
Me
NH2 OH
H2 / Pd-C
Me
Ph
Me
Me
Ph
C=N reduced by addition of H2 to the least hindered face
O
b
Me
N
Me
Ti3+ (aq)
OH
Me
Ph
Me
Ph
page 5
Ph
Cl
Reduction and ring opening reactions of cycloadducts
HN
Ph
H Ph
Ph
NH
Ph
NH
Ph
Ph
N
+ +N
Ph
Ph
Work out the dipole and dipolarophile combination that could be used to make
the cycloadducts given below, and......Draw the precursors and reagent(s)
needed to generate the dipoles you have identified.
6.
Me
HO
N
H
Bu
Me
O
c
Modules 06710-12-14
NH2 OH
LiAlH4
Me
Ph
Me
Me
Ph
C=N reduced by addition to the least hindered face
Me
O
d
HN
Me
Me
Ph
Ph
7.
Me
NaBH4
Identify the missing dipoles, dipolarophiles and cycloadducts in the schemes

below
O
CH2Ph
OH
N
a
Et
i, NaOCl
O
Et
ii, Et3N
CH2Ph
Et
Ph
Ph
i, NaNO2/ HCl
NH2
Ph
Ph
Ph
N
ii, NaN3
Ph
Ph
CN
CN
i, NaNO2/HCl
NH2
heat
ii, NaN3
N
N
Ph
NH
HN
Ph
N
i, POCl3
ii, Et3N
Ph
CO2Et
O
O
page 6
N
CO2Et
EtO2C
CO2Et
i, Cl2
ii, Et3N
OH
Modules 06710-12-14
NH2OH
H3C
H3 C
CH3
iii.
N
CH3
H3C
CH3
H3 C
NO2
excess PhNCO
Ph
H
O
Ph
O
OH
i, NCS
N
EtO2C
O
EtO2C
O
CO2Et
ii, Et3N
Ph
O
optically active dipolarophile produces
two diasteroisomeric products
O
CO2Et
Me
BuNHOH
H
Bu
N
Me
Bu
(exo)
H
CHO
Ph
Me
N
PhNHOH
N
O
O
H
page 7
Ph
Modules 06710-12-14
H
PhCH2
O
PhCH2
N
H
PhCH2
MeO2C
CO2Me
(exo)
OH
CO2Me
(exo)
(endo)
CH2
OMe
H
OMe
HCl
H
H
H
N
NHOH
(exo)
Ph
Ph
NH
N
l
Ph
Ph
N
heat
HN
H
Ph
Ph
page 8
8.
Modules 06710-12-14
The energies of the frontier molecular orbitals of two alkenes, G and H, and
benzonitrile oxide are given below. Sketch a labelled energy diagram and
indicate on it the major frontier orbital interactions between the dipole and both
dipolarophiles. Work out from your diagram which dipolarophile will react
preferentially with the dipole.
HOMO
(eV)
-10.8
-12.6
-9.4
Alkene G
Alkene H
Benzonitrile oxide
LUMO
(eV)
+2.0
+1.5
-0.50
Answer:
Ph C N O
+3
+2.0 eV
+2
+1
0
ALKENE G
-0.5 eV
ALKENE H
+1.5 eV
LUMO
= 11.4 eV
= 10.9 eV
-1
-2
-3
FMO energy
E / eV
-4
-5
-6
-7
-8
= 10.3 eV
-9
-10
-11
= 12.1 eV
-9.4 eV
-10.8 eV
HOMO
-12
-13
-12.6 eV
The smallest FMO energy gap, 10.3 eV, is between the LUMOdipole and HOMOalkene G
and so the reaction with G is faster than with alkene H.
page 9

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HETEROCYCLIC CHEMISTRY Part 3

DIPOLAR CYCLOADDITION CHEMISTRY

Identify the dipole structures from the reagents given

HETEROCYCLIC CHEMISTRY Part 3

HETEROCYCLIC CHEMISTRY Part 3

Identify the dipolarophile in the following reactions and give their

Identify the cycloadducts from the following reactants showing the

HETEROCYCLIC CHEMISTRY Part 3

HETEROCYCLIC CHEMISTRY Part 3

C=N reduced by addition of H2 to the least hindered face

Reduction and ring opening reactions of cycloadducts

HETEROCYCLIC CHEMISTRY Part 3

C=N reduced by addition to the least hindered face

Identify the missing dipoles, dipolarophiles and cycloadducts in the schemes

HETEROCYCLIC CHEMISTRY Part 3

HETEROCYCLIC CHEMISTRY Part 3

HETEROCYCLIC CHEMISTRY Part 3

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