Chemistry Reference
In-Depth Information
R
R
NN
R
R
MeO
OMe
Pd
O
Cl
O
Ph
R=
Ph
[Pd(IPr*
OMe
)(acac)Cl]
887
Structure of [Pd(IPr*
OMe
)(acac)Cl] (87).
Figure 4.38
[Pd(IPr*)(acac)Cl] (85), LiHMDS
or
[Pd(IPr*
OMe
)(acac)Cl] (87), KOtAm
O
Cl
N
+
H
N
O
1,4-dioxane, 110°C
[Pd] = 0.05 mol%
MeO
MeO
87, 5 min, GC Conv >99%
85,24h,GCConv=15%
[Pd(IPr*)(acac)Cl] (85), LiHMDS
or
[Pd(IPr*
OMe
)(acac)Cl] (87), KOtAm
Cl
NH
2
N
+
1,4-dioxane, 110°C
[Pd ] = 0.05 mol%
87,24h,GCConv>99%
85,24h,GCConv=0%
[Pd(IPr*)(acac)Cl] versus [Pd(IPr*
OMe
)(acac)Cl] in amination.
Scheme 4.63
R''
[Pd(IPr*)(cin)Cl] (9)
(1 mol%)
Cl
R''
N
+
H
N
R
R'
R
R'
KOtAm
a) RT, Solvent-free, Time
b) RT, DME, Time
N
N
H
N
H
N
H
MeO
a) 5 min: 98%
b) 24 h: 0%
a) 5 min: 96%
b) 24 h: 0%
a)24 h: 95%
b)24 h: 0%
a) 24 h: 94%
b) 24 h: 0%
Scheme 4.64
Solvent-free amination catalysed by [Pd(IPr*)(cin)Cl].
up at room temperature. Nevertheless, during the course of the reaction, a
strong exotherm was detected and promoted the coupling. There is a clear
danger associated with such an exotherm and special care should be taken
when attempting the reactions. The nature of the precatalysts used in the
reaction was investigated. Bulky ligands were found to be essential to
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