Chemistry Reference
In-Depth Information
Table 4.28 C-N bond formation using amides and formamides
as substrates.
R' '
[Pd(IPr)(Im)Cl
2
](16a)
(1 mol%)
Cl
O
R''
N
+
N
R'
R
R
H
R'
KOtBu, THF o r DMF, RT
Entry
Solvent
R
Amide
Yield (%)
O
1
THF
4-OMe
91
N
H
O
2
THF
4-Me
10
N
H
O
3
DMF
4-Me
72
N
H
O
4
DMF
4-H
99
N
H
O
5
THF
4-CN
70
N
H
O
6
THF
4-OMe
92
N
O
H
Ph
O
7
a
THF
3-OMe
92
N
H
H
O
8
THF
4-OMe
92
N
H
O
9
b
THF
3-OMe
86
N
H
a
Refluxing THF.
b
50 1C.
chlorides with a small range of amines. The reaction conditions were typical,
using 1 mol% of precatalyst at 70-90 1C in dioxane for 3 h and KOtBu as the
base, affording the expected coupled products in excellent yields.
Interestingly, this complex was also found to create C-N bonds using
amides and formamides as substrates (Table 4.28).
184
KOtBu was found to be
important to release the amine in the reaction medium. The use of amides
or formamides instead of the classical amines allowed milder reaction
conditions to be used. The reaction thus occurred at room temperature or
with gentle heating.
4.3.6.1.3 Carbonylative Amination. In 2012, Orellana and co-workers re-
ported a palladium-catalysed carbonylative amination reaction of iodides
with pyrrole (Scheme 4.67).
185
Different Pd-phosphine systems were
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