Chemistry Reference
In-Depth Information
Ph
Ph
Ru
3
(CO)
12
,
CO,
Δ
N
N
O
O
+
O
O
N
N
O
3.50
3.51
3.52
Scheme 3.26
O
O
Me
N
Me
N
Pd(OAc)
2
,
Cu(OAc)
2
, py
NMe
NMe
+
OHC
S
N
S
N
Me
O
Me
O
OHC
3.53
3
5
3
.
reductive
elimination
Pd(OAc)
2
C-H activation
O
Me
N
C-H activation
- AcOH
NMe
Pd
OHC
PdOAc
N
S
Me
O
S
3.56
3.57
CHO
Scheme 3.27
one. The mechanism appears to go through electrophilic attack of palladium(II) on the heterocycle to give a
thiophenyl palladium(II) complex
3.56
, which then preferentially reacts with a molecule of caffeine, perhaps
due to a coordination effect.
An electrophilic fluorinating agent
3.60
was employed as the oxidant to coupling benzamides
3.58
with
unactivated arenes (Scheme 3.28).
26
3.2 Aldehydes
Transition metals, especially rhodium(I) will undergo oxidative addition to the C-H bond of an aldehyde.
While this can result in decarbonylation (Section 4.7), alkene insertion can occur.
27
In an intramolecular
F
N
[O] =
OTf
ArHN
Me
ArHN
Me
O
3.60
O
Pd(OAc)
2
, [O]
+
F
Me
F
CF
3
3.58
3.59
Ar =
Me
F
F
Scheme 3.28
