Chemistry Reference
In-Depth Information
AgNO
3
+
N
N
N
Me
MeO
Me
Cl
MeOH, Δ
Me
MeO
88
89
(43%)
90
(0%)
SCHEME 10.12.
octane
as a single, as yet stereochemically unassigned, diastereomer (Scheme
10.12). Intriguingly, solvolysis of cyclohexene
91
, under the same reaction conditions,
led to a considerably more complex outcome (Scheme 10.13).
Gassman proposed that heterolysis of
89
91
by Ag(I) generated singlet nitrenium
species
93
. A facile 1,2-hydrogen shift would lead to iminium ion
94
, which, upon
hydrolysis, would produce aldehyde
98
. On the other hand, concerted intramolecular
Cl
N
NMe
NMe
Me
Me
N
AgNO
3
MeOH
Cl
THF aq.
D
92
(13%)
91
93
S
o
94
Intersystem
crossing
MeOH
H
2
O
NMe
CHO
Me
N
Me
N
MeO
95
(15%)
96;
T
1
98
(13 -18%)
97
H-atom
abstraction
H
2
O
NHMe
Me
Me
Me
N
N
N
OH
OH
99
(14 -17%)
100
(13-16%)
101
(11-14%)
102
(16-19%)
SCHEME 10.13.
