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O
Pd(dba)
2
(5 mol%)
CO (41 bar), NEt
3
(1 equiv)
100
o
C, 14-24 h
Up to 95% yield
CH
3
CN-benzene
R'
R
O
I
O
O
Pd(OAc)
2
-PPh
3
(5 mol%)
CO (41 bar ), NE t
3
(5 eq uiv)
100
R
R'
O
O
O
o
C, 14-24 h
CH
3
CN
58%
3a
3b
Scheme 10.3 First Pd-catalysed intramolecular carbonylative Heck reaction.
O
Pd( OAc)
2
(5 mol%)
PP h
3
(20 mol%)
CO (20-30 bar)
K
2
CO
3
(3 equiv)
DMF, 120
o
C, 20 h
X
CO
2
Me
CO
2
Me
Up to 87 % yield
R' = alkyl
H
R'
R"
H
R'
R"
X=I,Br
Scheme 10.4 Pd-catalysed carbonylative Heck reaction to give quinolinones.
O
R
O
PdCl
2
(PPh
3
)
2
(1mol%)
CO (15 b ar), benzene
NEt
3
(2.5 ml), 120
I
6 examples
65-7 5%
R''
R''
o
C, 18 h
O
R
R'
R'
Scheme 10.5 Pd-catalysed carbonylative cross-coupling reactions of aryl iodides
with alkynones to give furans.
Notably, Torii et al. reported the intramolecular carbonylative Heck
coupling of 3-(2-haloarylamino)prop-2-enoates to the corresponding quino-
linone derivatives.
8
In the presence of Pd(OAc)
2
under a CO atmosphere of
20 bar at 120 1C, quinolinones were synthesized in good yields
(Scheme 10.4). A related carbonylative cross-coupling of aryl iodides with
alkynones was reported by Miura and co-workers.
9
They showed that in the
presence of CO and a palladium catalyst, various furans were produced in
good yields (Scheme 10.5).
In 1995, Miura and co-workers reported a palladium-catalysed carbony-
lative cross-coupling of aryl iodides with five-membered cyclic olefins.
10
This
represents the first palladium-catalysed intermolecular carbonylative cross-
coupling of aryl iodides with olefins. Various benzoylated cyclic olefins were
isolated in good yields (Scheme 10.6). Unfortunately, the reaction with
cyclopentene led to a mixture of three regioisomers of benzoylcyclopentene.
During their investigations, Miura's group found that the amount of PPh
3
added to the reaction mixture markedly influenced the product yields.
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