Iridium complex-catalyzed carbonylation of allylic phosphates

Article abstract of DOI:10.1016/S0022-328X(02)01370-0

[Ir(cod)Cl]₂ with a ligand such as P(2-furyl)₃, PPh₂C₆F₅ or AsPh₃ showed high catalytic activity for the carbonylation of allylic phosphates in the presence of alcohols to give the corresponding β,γ-unsaturated esters. The carbonylation of diethyl (E)-3-phenyl-2-propenyl phosphate in the presence of EtOH under an initial carbon monoxide pressure of 40 kg cm^-2 at 100°C gave ethyl (E)-4-phenyl-3-butenoate in 90% yield. No (Z)-isomer was obtained. The reaction proceeded smoothly without using an amine as an additive. The carbonylation of 2-alkenyl diethyl phosphates in the presence of EtOH gave a mixture of ethyl (E)- and (Z)-3-alkenoate. The stereochemistry of the starting material was lost by syn-anti isomerization of the π-allyl iridium intermediate prior to the insertion of carbon monoxide into the iridium-carbon bond. Increasing the steric bulkiness of the substituent at the γ-position of the allyl system or increasing the initial carbon monoxide pressure increased the selectivity for a product with the same stereochemistry as the starting material.

Full text of DOI:10.1016/S0022-328X(02)01370-0

Journal of Organometallic Chemistry 651 (2002) 137ꢁ145
/
www.elsevier.com/locate/jorganchem
Iridium complex-catalyzed carbonylation of allylic phosphates
Ryo Takeuchi *, Yasushi Akiyama
Department of Chemistry, Graduate School of Integrated Science, Yokohama City University, 22-2, Seto, Kanazawa-ku, Yokohama 236-0027, Japan
Received 16 January 2002; received in revised form 12 February 2002; accepted 28 February 2002
Abstract
[
Ir(cod)Cl] with a ligand such as P(2-furyl) , PPh C F or AsPh showed high catalytic activity for the carbonylation of allylic
2 3 2 6 5 3
phosphates in the presence of alcohols to give the corresponding b,g-unsaturated esters. The carbonylation of diethyl (E)-3-phenyl-
ꢀ
2
2
-propenyl phosphate in the presence of EtOH under an initial carbon monoxide pressure of 40 kg cm at 100 8C gave ethyl (E)-4-
phenyl-3-butenoate in 90% yield. No (Z)-isomer was obtained. The reaction proceeded smoothly without using an amine as an
additive. The carbonylation of 2-alkenyl diethyl phosphates in the presence of EtOH gave a mixture of ethyl (E)- and (Z)-3-
anti isomerization of the p-allyl iridium intermediate prior
alkenoate. The stereochemistry of the starting material was lost by syn ꢁ
/
to the insertion of carbon monoxide into the iridiumÃcarbon bond. Increasing the steric bulkiness of the substituent at the g-
/
position of the allyl system or increasing the initial carbon monoxide pressure increased the selectivity for a product with the same
stereochemistry as the starting material. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Iridium; Carbonylation; Allylic phosphates; syn ꢁanti Isomerization; b,g-Unsaturated esters; p-Allyl iridium
/
1
. Introduction
Synthetic reactions that include p-allyl metal inter-
As the selectivity of iridium complex-catalyzed allylic
substitution is quite different from that of a palladium
complex-catalyzed reaction, an iridium complex catalyst
is a useful complement to a palladium complex catalyst.
Recently, a few examples of iridium complex-cata-
lyzed carbonylation have been reported [8]. An iridium
complex is attractive as a new and efficient catalyst for
carbonylation. These results prompted us to study the
iridium complex-catalyzed carbonylation of allylic es-
ters. In this paper, we report the first example of an
iridium complex-catalyzed carbonylation of allylic esters
in the presence of alcohols.
mediates have been extensively studied and used to
construct complex organic molecules. The reaction of a
p-allyl metal intermediate with nucleophiles is recog-
nized as one of the most useful synthetic reactions [1].
Another important version of this reaction is an
insertion reaction into a metalÃ
allyl ligand [2]. The insertion of carbon monoxide into a
transition metalÃcarbon bond is a fundamental step for
introducing a carbonyl group into an organic molecule
3]. The reaction of a p-allyl metal intermediate with
/
carbon bond of the p-
/
[
carbon monoxide has attracted much attention. Cataly-
tic carbonylation of allylic esters and halides in the
presence of alcohols is the most straightforward method
for preparing b,g-unsaturated esters. Several transition
metal complexes such as with palladium [4], rhodium [5]
and ruthenium [6] have been shown to be efficient
catalysts for this carbonylation.
2
. Results and discussion
2.1. Carbonylation of 3-aryl-2-propenyl diethyl
phosphates
Various allylic compounds such as allylic esters
We were the first to show that an iridium complex
could be an efficient catalyst for allylic substitution [7].
[
4a,e,g,h,k,l], allylic alcohols [4bꢁd], allylic amines [4f]
/
and allylic ethers [4j,o] have been used as substrates for
carbonylation. In this study, an allylic compound was
carbonylated in the presence of five equivalents of EtOH
*
E-mail address: rtakeuch@yokohama-cu.ac.jp (R. Takeuchi).
Corresponding author. Tel./fax: ꢃ81-45-787-2218.
/
and a catalytic amount of [Ir(cod)Cl] and PPh (P/Irꢂ
/
2
3
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 3 7 0 - 0

138
R. Takeuchi, Y. Akiyama / Journal of Organometallic Chemistry 651 (2002) 137ꢁ145
/
Table 1
Carbonylation of 1
in Table 2. Reactions were carried out at 100 8C for 24 h
under an initial carbon monoxide pressure of 40 kg
a
ꢀ
2
cm . The ratio of phosphorous atom to Ir atom was
b
Entry
Substrate
Conditions
Yield (%)
important. The reaction at a P/Ir ratio of 1 gave 3a in
80% yield (entry 1). The reaction at a P/Ir ratio of 2
3
a
4a
decreased the yield of 3a slightly, but increased the yield
of 4a (entry 2). Based on this result, we examined the
effects of various phosphorous ligands on carbonylation
at a P/Ir ratio of 1. Phosphine, which is a more electron-
1
2
3
4
5
1a XꢂOPO(OEt)
2
100 8C 24 h
160 8C 24 h
160 8C 24 h
160 8C 24 h
100 8C 24 h
80
29
3
2
1
2
6
0
1b XꢂOCO
1c XꢂOAc
1d XꢂOH
1e XꢂCl
2
Et
34
0
donating ligand than PPh , decreased the yield of 3a
3
a
(entries 3 and 4). These donating ligands increased the
yield of 4a. Electron-withdrawing ligands such as
PPh C F , P(2-furyl) and AsPh3 gave good results
A mixture of 1a (3 mmol), EtOH (15 mmol), [Ir(cod)Cl]
2
(0.06
mmol), PPh
3
(0.12 mmol) and dioxane (10 ml) was stirred under an
ꢀ
2
initial carbon monoxide pressure of 40 kg cm
b
Isolated yield.
.
2
6
5
3
(entries 5ꢁ/7). Although P(OPh) was an efficient ligand
3
for iridium complex-catalyzed allylic substitution [7],
P(OPh) gave 3a in 47% yield (entry 8). P(OEt) gave a
result comparable to that with PPh3 (entry 9). The
catalytic activities of several Ir complexes with AsPh3
1
cm
) under an initial carbon monoxide pressure of 40 kg
3
3
ꢀ
2
(Eq. (1)). The results are summarized in Table 1.
Phosphate 1a was smoothly carbonylated. Carbonate
b, which was a good substrate for palladium complex-
1
(As/Irꢂ/1) were examined. [Ir(cot) Cl] showed a cata-
2 2
and ruthenium complex-catalyzed carbonylation, gave
product in 29% yield (entry 2) [4l,6]. Acetate 1c, alcohol
lytic activity comparable to that of [Ir(cod)Cl] (entry
2
11), while Ir(cod)(acac) and [Ir(cod) ]BF were less
efficient than [Ir(cod)Cl] (entries 10 and 12). Ir (CO)
2 4
1
d and halide 1e gave a product in low yields (entries 3ꢁ
/
2
4
12
5). No (Z)-3a was obtained. Conversions of 1bꢁd were
low, but 1e was completely consumed.
/
showed no catalytic activity (entry 13).
The effect of the solvent on the carbonylation of 1a
was examined. Five equivalents of EtOH to 1a were
used. The results are summarized in Table 3. Dioxane
gave the best results (entry 1). Palladium complex-
catalyzed carbonylation of allylic phosphates was car-
ried out using EtOH as a solvent [4a,h,k], but this
decreased the yield of 3a (entry 5).
ð1Þ
The effects of the initial carbon monoxide pressure
and reaction temperature on the reaction of 1a were
examined. The results are summarized in Table 4. The
reaction under carbon monoxide atmosphere did not
The effect of a ligand on the carbonylation of
phosphate 1a was examined. The results are summarized
Table 2
Effect of catalyst on carbonylation of 1a
a
b
Entry
Catalyst
Ligand
P or As/Ir
Yield (%)
3
a
4a
1
2
3
4
5
6
7
8
[Ir(cod)Cl]
[Ir(cod)Cl]
[Ir(cod)Cl]
[Ir(cod)Cl]
[Ir(cod)Cl]
[Ir(cod)Cl]
[Ir(cod)Cl]
[Ir(cod)Cl]
[Ir(cod)Cl]
2
2
2
2
2
2
2
2
2
PPh
PPh
3
1
2
1
1
1
1
1
1
1
1
1
1
1
80
76
35
68
86
88
90
47
80
32
89
77
0
2
8
3
P(n-Bu)
3
22
9
PPh
PPh
2
Me
2
C
6
F
5
3
P(2-furyl)
AsPh
P(OPh)
P(OEt)
3
0
3
0
3
10
1
9
3
c
1
1
1
1
0
1
2
3
[Ir(cod)
[Ir(cot)
Ir(cod)(acac)
Ir (CO)12
2
]BF
4
AsPh
AsPh
AsPh
AsPh
3
3
3
3
53
1
2
Cl]
2
c
2
d
4
0
a
A mixture of 1a (3 mmol), EtOH (15 mmol), Ir complex (0.06 mmol), ligand and dioxane (10 ml) was stirred under an initial carbon monoxide
ꢀ
2
pressure of 40 kg cm
b
at 100 8C for 24 h.
Isolated yield.
Ir complex (0.12 mmol).
Ir complex (0.03 mmol).
c
d

R. Takeuchi, Y. Akiyama / Journal of Organometallic Chemistry 651 (2002) 137ꢁ
/145
139
Table 3
Effect of a solvent on carbonylation of 1a
equivalents of an alcohol to 1a were used. Carbonyla-
tion of 1a in the presence of n-hexanol (2b) or i-PrOH
(2c) gave the product in a yield comparable to that in the
presence of EtOH (2a) (entries 2 and 3). A functiona-
lized alcohol such as methyl glycolate (2d) gave the
corresponding product 3d in 52% yield (entry 4). The
electron-withdrawing property of an ester group should
reduce the nucleophilicity of an alcohol, thereby de-
creasing the yield of 3. Carbonylation of 1a in the
presence of tert-BuOH (2e) did not give the correspond-
ing product 3e. Steric bulkiness of tertiary alcohol would
retard nucleophilic attack to an acyl group on the metal
[9].
a
b
Entry
Solvent
Yield (%)
3
a
4a
1
2
3
4
5
Dioxane
Benzene
90
86
85
29
53
0
3
1,2-Dichloropropane
MeCN
EtOH
1
25
22
a
A mixture of 1a (3 mmol), EtOH (15 mmol), [Ir(cod)Cl]
2
(0.06
mmol), AsPh
3
(0.12 mmol) and solvent (10 ml) was stirred under an
ꢀ
2
initial carbon monoxide pressure of 40 kg cm
b
Isolated yield.
at 100 8C for 24 h.
Table 4
Effect of carbon monoxide pressure and reaction temperature on
ð2Þ
a
carbonylation of 1a
Entry Initial CO pressure (kg cmꢀ
2
)
Temperature ( 8C) Yield
b
(
%)
3
a
4a
It is well known that carbonylation in the presence of
water gives the corresponding carboxylic acid. Carbo-
nylation of 1a in the presence of five equivalents of
water under an initial carbon monoxide pressure of 40
kg cm at 100 8C for 24 h did not give the correspond-
ing carboxylic acid, but phosphate 1a was completely
consumed.
1
2
3
4
5
1
5
100
100
100
100
60
0
0
0
0
0
0
93
90
90
0
20
40
20
ꢀ2
a
A mixture of 1a (3 mmol), EtOH (15 mmol), [Ir(cod)Cl]
mmol), AsPh
carbon monoxide pressure for 24 h.
2
(0.06
3
(0.12 mmol) and dioxane (10 ml) was stirred under
Carbonylation of (E)-3-aryl-2-propenyl diethyl phos-
phate (5) was carried out under the same reaction
conditions as with 1a (Eq. (3)). Phosphate 5a was
smoothly carbonylated to give 6a in 81% yield, whereas
the carbonylation of phosphate 5b gave 6b in 65% yield.
Introducing an electron-withdrawing group on an aro-
matic ring decreased the product yield.
b
Isolated yield.
give 3a (entry 1). Phosphate 1a was recovered in
quantitative yield. The carbon monoxide pressure is
essential for obtaining 3a. The reaction at 60 8C did not
give 3a (entry 5).
Phosphate is a leaving group in this carbonylation. As
the reaction proceeds to give 3a, diethyl phosphate is
formed to make the reaction mixture acidic. The use of
an amine can scavenge liberated diethyl phosphate to
make the reaction mixture neutral. In palladium com-
plex-catalyzed carbonylation of allylic phosphate, it is
well known that the use of an amine is necessary to
obtain a product in high yield [4h,k]. With this
carbonylation, the use of an amine resulted in a decrease
in the yield of 3a. The reaction of 1a in the presence of
ð3Þ
five equivalents of EtOH and 1.2 equivalents of Et N
3
under an initial carbon monoxide pressure of 40 kg
ꢀ
2.2. Carbonylation of 3-substituted-2-propenyl diethyl
phosphates
2
cm at 100 8C for 24 h gave 3a in 69% yield. When (i-
Pr) NEt or pyridine was used in place of Et N, the yield
2
3
of 3a was 21 and 5%, respectively. Carbonylation
without an amine gave a better result than that with
an amine. The coordination of an amine might saturate
the metal center to reduce the catalytic activity.
The carbonylation of diethyl (E)-2-nonenyl phos-
phate ((E)-7a) in the presence of EtOH under an initial
ꢀ
2
carbon monoxide pressure of 40 kg cm
at 100 8C for
24 h gave an 88:12 mixture of (E)- and (Z)-ethyl 3-
decenoate ((E)- and (Z)-8a) in 69% yield (Table 6; entry
1) (Eq. (4)). Carbonylation of (Z)-7a under the same
Various alcohols could be used for the carbonylation
Eq. (2)). The results are summarized in Table 5. Five
(

140
R. Takeuchi, Y. Akiyama / Journal of Organometallic Chemistry 651 (2002) 137ꢁ
/145
Table 5
Carbonylation of 1a
a
b
Entry
Alcohol
Product
Yield (%)
1
2
3
4
2a RꢂEt
2b RꢂCH
2c Rꢂ(CH
2d RꢂCH
3a
3b
3c
3d
90
85
82
52
3
(CH
CH
CCH
2
2 5
)
3 2
)
3
O
2
a
A mixture of 1a (3 mmol), alcohol (15 mmol), [Ir(cod)Cl]
2
(0.06
mmol), AsPh
3
(0.12 mmol) and dioxane (10 ml) was stirred under an
ꢀ
2
initial carbon monoxide pressure of 40 kg cm
b
Isolated yield.
at 100 8C for 24 h.
reaction conditions gave a similar result (entry 2). Both
reactions gave the corresponding (E)-ester as a major
product regardless of the stereochemistry of the starting
material.
ð4Þ
Scheme 1.
The loss of the stereochemistry of the starting
seems to be shifted toward 10. Therefore, (E)-8 is
obtained as a major product.
Intermediates 11 and 12 are sterically more congested
than 9 and 14, since an iridium metal is attached to a
secondary carbon. When the substituent at C-1 is
material can be explained by syn ꢁ/anti isomerization
[
10] of the p-allyl Ir intermediate (Scheme 1). Oxidative
addition of (E)-7a gives s-allyl intermediate 9 [11]. s-p-
s Interconversion of 9 gives s-allyl intermediate 11.
Rotation around the C1Ã
p-s interconversion gives s-allyl intermediate 14. Inser-
tion of CO into the C3ÃIr bond in 14 followed by
/
C2 bond in 11 followed by s-
sterically bulky, we can expect that syn ꢁ
tion is decelerated. This would lead to the insertion of
CO into the IrÃC3 bond in intermediate 9 or 14 prior to
syn ꢁanti isomerization. If this hypothesis is correct, the
/
anti isomeriza-
/
/
nucleophilic attack by the alcohol gives (Z)-8. It is well
known that a syn p-allyl metal complex is thermodyna-
mically more stable than the corresponding anti p-allyl
metal complex [12]. The equilibrium between 10 and 13
/
carbonylation of phosphate 7 bearing a sterically bulky
substituent at the g-position should increase the selec-
tivity for a product with the same stereochemistry as the
starting material.
We examined the carbonylation of phosphate bearing
a secondary alkyl group at the g-position in the allyl
system. The results are summarized in Table 6. Carbo-
nylation of (E)-7b, where a cyclohexyl group is sub-
stituted at the g-position, in the presence of EtOH under
Table 6
Carbonylation of 7
a
b
c
Entry Substrate
Yield of 8 (%)
Ratio E/Z
1
2
3
4
5
6
(E)-7a Rꢂn-Hex
(Z)-7a Rꢂn-Hex
(E)-7b Rꢂcyclohexyl
(Z)-7b Rꢂcyclohexyl
(E)-7c RꢂCH
(Z)-7c RꢂCH
69
77
64
68
88:12
71:29
93:7
ꢀ
2
an initial carbon monoxide pressure of 40 kg cm
at
1
00 8C for 24 h gave a 93:7 mixture of (E)- and (Z)-8b in
4% yield (entry 3). As expected, the selectivity for the
62:38
95:5
6
3
(CH
2
)
3
CH(Et) 55
CH(Et) 66
(
E)-ester increased. Similarly, carbonylation of (E)-7c in
3
(CH
2
)
3
37:63
the presence of EtOH under the same reaction condi-
tions gave a 95:5 mixture of (E)- and (Z)-8c in 55% yield
(entry 5). Carbonylation of (Z)-phosphate bearing a
secondary alkyl group at the g-position in the allyl
system is expected to increase the selectivity for (Z)-8.
a
A mixture of 7 (3 mmol), EtOH (15 mmol), [Ir(cod)Cl]
mmol), AsPh
2
(0.06
(0.12 mmol) and dioxane (10 ml) was stirred under an
3
ꢀ
2
initial carbon monoxide pressure of 40 kg cm
b
at 100 8C for 24 h.
Isolated yield.
Determined by H-NMR.
c
1

R. Takeuchi, Y. Akiyama / Journal of Organometallic Chemistry 651 (2002) 137ꢁ
/145
141
The carbonylation of (Z)-7b in the presence of EtOH
under the same reaction conditions gave a 62:38 mixture
of (E)- and (Z)-8b in 68% yield (entry 4). The selectivity
for (Z)-ester was increased compared to that in the
carbonylation of (Z)-7a. Changing the substituent at the
g-position from a cyclohexyl group to a 1-ethylpentyl
group increased the selectivity for the (Z)-ester. Carbo-
nylation of (Z)-7c in the presence of EtOH under an
initial carbon monoxide pressure of 40 kg cmꢀ at
equilibrium between the s-allyl intermediate and p-allyl
intermediate toward the s-allyl intermediate. Carbon
monoxide at high pressure might also promote the
insertion of carbon monoxide prior to sꢁp interconver-
/
sion, leading to retention of stereochemistry.
Finally, we examined the reaction of regioisomeric
phosphate 17 (Eq. (5)). Carbonylation of 17 in the
presence of EtOH gave an 89:11 mixture of (E)- and
(Z)-18 in 55% yield. No 19 was obtained. Oxidative
addition of 17 gives intermediate 11 or 12 (Scheme 1).
2
1
00 8C for 24 h gave a 37:63 mixture of (E)- and (Z)-8c
in 66% yield (entry 6). The selectivity for (Z)-8c was
greater than that for (E)-8c. Notably, the (Z)-ester was
obtained as a major product. The Z stereochemistry of
the starting material was retained to some extent.
The initial pressure of carbon monoxide affected the
stereoselectivity of the carbonylation of 2-alkenyl
Insertion of CO into the IrÃ
/
C1 bond seems to be more
difficult than that into the IrÃ
/C3 bond, since the C1
carbon is more sterically congested than the C3 carbon.
Therefore, a product was obtained from 9 and 14.
diethyl phosphate (7aꢁc). The results are summarized
/
in Table 7. In the case of (E)- and (Z)-7a, the selectivity
for a product with the same stereochemistry as the
starting material increased as the initial pressure of
carbon monoxide increased [13]. The selectivity for (E)-
ð5Þ
8
a increased from 84 to 90% (entries 1ꢁ
selectivity for (Z)-8a also increased from 21 to 37%
entries 5ꢁ8). The carbonylation of 7b and 7c showed
/
4). The
(
/
the same tendency.
The effect of the initial pressure of carbon monoxide
on stereoselectivity can be explained as follows. Carbon
monoxide at high pressure coordinates to the iridium
center to saturate the coordination site. It shifts the
In conclusion, an iridium complex is an efficient
catalyst for the carbonylation of allylic phosphates in
Table 7
Effect of carbon monoxide pressure on carbonylation of 7
a
Initial CO pressure (kg cmꢀ
)
2
Yield of 8 (%)
b
Ratio E/Z
c
Entry
Substrate
1
2
3
4
5
6
7
8
9
(E)-7a Rꢂn-Hex
5
20
40
90
5
70
70
69
68
80
69
77
61
60
64
64
73
68
69
74
55
47
74
72
66
60
84:16
87:13
88:12
90:10
79:21
70:30
71:29
63:37
91:9
(Z)-7a Rꢂn-Hex
20
40
90
5
(E)-7b Rꢂcyclohexyl
(Z)-7b Rꢂcyclohexyl
1
1
1
1
1
1
1
1
1
1
2
2
0
1
2
3
4
5
6
7
8
9
0
1
40
90
5
93:7
94:6
82:18
62:38
55:45
95:5
40
90
5
3 2 3
(E)-7c RꢂCH (CH ) CH(Et)
40
90
5
95:5
95:5
(Z)-7c RꢂCH
3
(CH
2
)
3
CH(Et)
49:51
37:63
37:63
37:63
20
40
90
a
2 3
A mixture of 7 (3 mmol), EtOH (15 mmol), [Ir(cod)Cl] (0.06 mmol), AsPh (0.12 mmol) and dioxane (10 ml) was stirred under carbon monoxide
pressure at 100 8C for 24 h.
Isolated yield.
b
c
1
Determined by H-NMR.

142
R. Takeuchi, Y. Akiyama / Journal of Organometallic Chemistry 651 (2002) 137ꢁ145
/
the presence of alcohols. Iridium complex-catalyzed
carbonylation has rarely been studied. This success
should offer a new approach to iridium complex-
catalyzed organic synthesis.
0.88 (t, Jꢂ
(m, 2H), 4.10 (d, Jꢂ
Hz, 1H), 5.58 (dt, Jꢂ
MHz, CDCl ) d 11.6, 14.0, 22.8, 27.7, 29.4, 34.4, 44.0,
/
7.2 Hz, 3H), 1.16ꢁ
/
1.46 (m, 8H), 1.83ꢁ
15.4, 8.7
15.4, 5.2 Hz, 1H); C-NMR (100
/
1.88
/
5.2 Hz, 2H), 5.41 (dd, Jꢂ
/
1
3
/
3
63.7, 128.8, 137.5.
3
. Experimental
3.2.2. (Z)-3-Cyclohexyl-2-propen-1-ol [17]
3
.1. General
To a solution of NaH (0.696 g, 29 mmol) in THF (100
ml) was added ethyl (diphenylphosphono)acetate (6.406
g, 20 mmol) dropwise at 0 8C. The mixture was stirred at
1
13
H-NMR and C-NMR spectra were measured on
Bruker AVANCE-400 spectrometer or JEOL EX-270
spectrometer using Me Si as an internal standard.
0 8C for 20 min, and the mixture was then cooled to ꢀ
/
78 8C for 10 min. Cyclohexanecarboxaldehyde (2.243 g,
20 mmol) was added, and the resulting mixture was
gradually warmed to room temperature for 21 h. Water
was added and the mixture was extracted with ether.
4
Samples were dissolved in CDCl or benzene-d solu-
3
6
tions. GC analyses were performed on a Shimadzu GC-
4A by using a 3 mmꢄ2 m glass columns packed with
1
/
either 5% PEG-HT on 60/80 mesh chromosorb w AW-
DMCS or 5% OV-17 on 60/80 mesh chromosorb w AW-
DMCS. Column chromatography was carried out on
70-230 mesh silica gel (Merck; silica gel 60). Elemental
analyses were performed at the Microanalytical Center
of Kyoto University.
The ether solution was dried with MgSO and evapo-
4
rated in vacuo. Medium-pressure column chromatogra-
phy (n-hexane) of the residue gave pure ethyl (Z)-3-
cyclohexyl-2-propenoate (yield 54%, 1.968 g). Reduction
of ethyl (Z)-3-cyclohexyl-2-propenoate by DIBALH
1
gave
(Z)-3-cyclohexyl-2-propen-1-ol.
H-NMR
1.73 (m,
6.7, 1.2 Hz, 2H),
(CDCl , 400MHz) d 1.04ꢁ
/
1.34 (m, 6H), 1.58ꢁ
/
3
3
.2. Materials
5H), 2.24ꢁ
/
2.33 (m, 1H), 4.20 (dd, Jꢂ
/
5
.40 (d, Jꢂ
/
10.8 Hz, 1H), 5.49 (dt, Jꢂ
/
10.8, 6.7 Hz, 1H);
1
3
All reagents and the solvents were dried and purified
C-NMR (100 MHz, CDCl ) d 25.8 (2C), 25.9 (2C),
3
before use by the usual procedures. Allylic phosphates
were prepared by the reaction of the corresponding
alcohols with diethyl chlorophosphate. (E)-3-Phenyl-2-
propen-1-ol, (E)-2-nonen-1-ol, (Z)-2-nonen-1-ol, 1-oc-
ten-3-ol, (E)-1-chloro-3-phenyl-2-propene and (E)-3-
phenyl-2-propenyl acetate were purchased. Ethyl (E)-
33.4, 36.6, 58.8, 126.5, 139.2.
3.2.3. (Z)-4-Ethyl-2-octen-1-ol
(Z)-4-Ethyl-2-octen-1-ol was prepared similarly to
give (Z)-1-cyclohexyl-2-propen-1-ol from 2-ethylhexa-
1
nal and ethyl (diphenylphosphono)acetate. H-NMR
3
-phenyl-2-propenyl carbonate was prepared by the
reaction of (E)-3-phenyl-2-propen-1-ol with ethyl cho-
loroformate. (E)-3-(4-Methylphenyl)-2-propen-1-ol,
E)-3-(4-fluorophenyl)-2-propen-1-ol and (E)-3-cyclo-
(C D , 400 MHz) d 0.80 (t, Jꢂ
/
7.4 Hz, 3H), 0.87 (t, Jꢂ
1.36 (m, 8H), 2.02ꢁ2.08 (m, 2H), 4.03
(br, 2H), 5.04 (t, Jꢂ10.7 Hz, 1H), 5.60 (dt, Jꢂ10.7, 6.3
Hz, 1H); C-NMR (100 MHz, C D ) d 12.0, 14.2, 23.2,
/
6
6
7.2 Hz, 3H), 1.01ꢁ
/
/
(
/
/
1
3
hexyl-2-propen-1-ol were prepared by the published
method [7a]. [Ir(cod)Cl] , [Ir(cot) Cl] and [Ir(cod) ]BF
4
6
6
28.8, 29.9, 35.5, 39.6, 59.0, 129.9, 136.8.
2
2
2
2
were prepared by the published method [14ꢁ
/16]. Ir(co-
d)(acac) and Ir (CO) were purchased.
4
12
3.3. General procedure for the carbonylation of allylic
phosphates
3
.2.1. (E)-4-Ethyl-2-octen-1-ol
To a solution of NaH (0.528 g, 22 mmol) in 1,2-
dimethoxyethane (40 ml) was added ethyl (diethylpho-
sphono)acetate (5.381 g, 24 mmol) dropwise at 0 8C.
The mixture was gradually warmed to room tempera-
ture for 10 min. 2-Ethylhexanal (2.564 g, 20 mmol) was
added, and the resulting mixture was stirred at room
temperature for 2 h. Water was added and the mixture
was extracted with ether. The ether solution was dried
A typical procedure is described (Table 2, entry 7). A
mixture of dioxane (10 ml), EtOH (0.691 g, 15 mmol), 1a
(0.811 g, 3 mmol), [Ir(cod)Cl] (40.3 mg, 0.06 mmol) and
2
AsPh (36.7 mg, 0.12 mmol) was placed in a 50 ml
3
stainless autoclave equipped with a glass liner and a
magnetic stirring bar. The reactor was sealed and was
flushed with carbon monoxide three times, and then it
ꢀ
2
with MgSO and evaporated in vacuo. Medium-pressure
4
was pressurized with carbon monoxide to 40 kg cm
.
column chromatography (n-hexaneꢁ
the residue gave pure ethyl (E)-4-ethyl-2-octenoate
yield 76%, 3.014 g). Reduction of ethyl (E)-4-ethyl-2-
octenoate by DIBALH gave (E)-4-ethyl-2-octen-1-ol.
/
AcOEtꢂ
/
95/5) of
The mixture was heated at 100 8C for 24 h. The reaction
was terminated by rapid cooling. The solvent was
evaporated in vacuo. Column chromatography (n-
(
hexaneꢁ
/
AcOEtꢂ98/2) of the residue gave 3a as a
/
1
H-NMR (CDCl , 400 MHz) d 0.84 (t, Jꢂ7.4 Hz, 3H),
/
colorless oil (yield 90%, 0.514 g).
3

R. Takeuchi, Y. Akiyama / Journal of Organometallic Chemistry 651 (2002) 137ꢁ
/145
143
3
3
.4. Characterization of products
137.2, 171.7. Anal. Calc. for C H O : C, 76.44; H,
13 16 2
7.90; O, 15.67. Found: C, 76.17; H, 7.85%.
.4.1. Ethyl (E)-4-phenyl-3-butenoate (3a) [4h]
1
H-NMR (CDCl , 400 MHz) d 1.26 (t, Jꢂ7.1 Hz,
/
3.4.7. Ethyl (E)-4-(4-fluorolphenyl)-3-butenoate (6b)
1
3
3
2
1
H), 3.22 (dd, Jꢂ
H), 6.29 (dt, Jꢂ15.9, 7.1 Hz, 1H), 6.47 (d, Jꢂ
H), 7.18ꢁ
/
7.1, 1.4 Hz, 2H), 4.16 (q, Jꢂ
/
7.1 Hz,
15.9 Hz,
H-NMR (CDCl , 400 MHz) d 1.27 (t, Jꢂ7.1 Hz,
/
3
/
/
3H), 3.22 (dd, Jꢂ
2H), 6.21 (dt, Jꢂ15.9, 7.1 Hz, 1H), 6.44 (d, Jꢂ
1H), 6.98 (t, Jꢂ8.7 Hz, 2H), 7.32 (dd, Jꢂ
2H). C-NMR (CDCl , 100 MHz) d 14.1, 38.3, 60.7,
/
7.1, 1.2 Hz, 2H), 4.17 (q, Jꢂ/7.1 Hz,
1
3
/
7.37 (m, 5H). C-NMR (CDCl , 100 MHz)
/
/
15.9 Hz,
3
d 14.1, 38.4, 60.6, 121.8, 126.2 (2C), 127.4, 128.4 (2C),
1
/
/8.7, 5.4 Hz,
1
3
33.3, 136.8, 171.4.
3
1
15.3 (d, JCÃFꢂ
127.7 (d, JCÃFꢂ
Hz), 162.2 (d, JCÃFꢂ
C H FO : C, 69.22; H, 6.29; F, 9.12; O, 15.37. Found:
/
21.6 Hz, 2C), 121.5 (d, JCÃFꢂ
8.0 Hz, 2C), 132.1, 133.0 (d, JCÃFꢂ
246.6 Hz), 171.5. Anal. Calc. for
/
1.9 Hz),
3
.4.2. n-Hexyl (E)-4-phenyl-3-butenoate (3b)
/
/3.3
1
H-NMR (CDCl , 400 MHz) d 0.88 (t, Jꢂ
/
6.8 Hz,
6.8 Hz, 2H),
6.8 Hz, 2H),
15.9 Hz, 1H),
7.37 (m, 5H). C-NMR (CDCl , 100 MHz) d
/
3
3H), 1.27ꢁ
3.23 (dd, Jꢂ
6.30 (dt, Jꢂ15.9, 7.1 Hz, 1H), 6.48 (d, Jꢂ
7.19ꢁ
1
1
/
1.38 (m, 6H), 1.63 (quintet, Jꢂ
/
1
2
13
2
/
7.1, 1.3 Hz, 2H), 4.10 (t, Jꢂ
/
C, 68.94; H, 6.17; F, 9.17%.
/
/
1
3
/
3.4.8. Ethyl (E)-3-decenoate ((E)-8a)
3
1
3.9, 22.4, 25.5, 28.5, 31.3, 38.4, 64.9, 121.8, 126.2 (2C),
27.4, 128.4 (2C), 133.2, 136.8, 171.5. IR (neat) 1737
H-NMR (C D , 400 MHz) d 0.86 (t, Jꢂ
/
7.1 Hz, 3H),
1.27 (m, 8H), 1.91 (q, Jꢂ
6.9, 1.0 Hz, 2H), 3.93 (q, Jꢂ
15.3, 6.7 Hz, 1H), 5.61 (dt, Jꢂ
5.3, 6.9 Hz, 1H). C-NMR (C D , 100 MHz) d 14.0,
6
6
0.94 (t, Jꢂ
6.7 Hz, 2H), 2.88 (dd, Jꢂ
7.1 Hz, 2H), 5.41 (dt, Jꢂ
/
7.1 Hz, 3H), 1.13ꢁ
/
/
ꢀ
1
cm . Anal. Calc. for C H O : C, 78.01; H, 9.00; O,
1
/
/
6
22
2
1
2.99. Found: C, 78.23; H, 9.10%.
/
/
1
3
1
6
6
3
.4.3. 2-Methylethyl (E)-4-phenyl-3-butenoate (3c)
14.1, 22.5, 28.7, 29.1, 31.6, 32.4, 38.1, 60.4, 121.5, 134.7,
ꢀ1
1
H-NMR (CDCl , 270 MHz) d 1.24 (d, Jꢂ
/
6.3 Hz,
7.1, 1.4 Hz, 2H), 5.03 (seventet, Jꢂ
.3 Hz, 1H), 6.29 (dt, Jꢂ15.9, 7.1 Hz, 1H), 6.47 (d, Jꢂ
5.9 Hz, 1H), 7.18ꢁ7.37 (m, 5H). C-NMR (CDCl3,
172.1. IR (neat) 1741 cm . Anal. Calc. for C H O :
12 22
3
2
6
6
1
6
1
H), 3.19 (dd, Jꢂ
/
/
C, 72.68; H, 11.18; O, 16.14. Found: C, 72.74; H,
11.37%.
/
/
1
3
/
7.8 MHz) d 21.7 (2C), 38.6, 68.0, 122.0, 126.2 (2C),
27.4, 128.4 (2C), 133.1, 136.9, 171.0. IR (neat) 1732
3.4.9. Ethyl (Z)-3-decenoate ((Z)-8a)
Compound (Z)-8a could not be isolated in pure form.
ꢀ
1
1
Partial H-NMR spectra was obtained from the mixture
cm . Anal. Calc. for C H O : C, 76.44; H, 7.90; O,
1
3
16
2
1
1
5.67. Found: C, 76.72; H, 8.14%.
of (E)-8a. H-NMR (400 MHz, C D ) d 2.97 (d, Jꢂ
/7.2
6
6
Hz, 2H), 5.48 (dt, Jꢂ
/
10.8, 7.3 Hz, 1H), 5.71 (dt, Jꢂ
/
3
.4.4. Methoxycarbonylmethyl (E)-4-phenyl-3-
butenoate (3d)
10.8, 7.2 Hz).
1
H-NMR (CDCl , 270 MHz) d 3.36 (dd, Jꢂ
/
7.1, 1.4
15.9, 7.1
7.38 (m, 5H).
3.4.10. Ethyl (E)-4-cyclohexyl-3-butenoate ((E)-8b)
3
1
Hz, 2H), 3.75 (s, 3H), 4.65 (s, 2H), 6.30 (dt, Jꢂ
Hz, 1H), 6.52 (d, Jꢂ15.9 Hz, 1H), 7.20ꢁ
/
H-NMR (C D , 400 MHz) d 0.94 (t, Jꢂ
/
7.1 Hz, 3H),
1.65 (m, 6H), 1.79ꢁ1.83 (m,
6.9 Hz, 2H), 3.93 (q, Jꢂ7.1 Hz, 2H),
15.5, 6.7 Hz, 1H), 5.58 (dt, Jꢂ15.5, 6.9
Hz, 1H). C-NMR (C D , 100 MHz) d 14.2, 26.3 (2C),
6
6
/
/
1.00ꢁ
1H), 2.88 (d, Jꢂ
5.38 (dd, Jꢂ
/
1.19 (m, 4H), 1.51ꢁ
/
/
1
3
C-NMR (CDCl , 67.8 MHz) d 37.6, 52.1, 60.7, 120.8,
/
/
3
126.2 (2C), 127.5, 128.4 (2C), 133.8, 136.6, 168.0, 170.8.
Anal. Calc. for C H O : C, 66.66; H, 6.02; O, 27.32.
Found: C, 66.92; H, 6.27%.
/
/
1
3
1
3
14
4
6
6
26.4, 33.1 (2C), 38.4, 40.9, 60.2, 120.2, 140.1, 171.3. IR
ꢀ
12 20 2
1
neat) 1740 cm . Anal. Calc. for C H O : C, 73.43;
(
H, 10.27; O, 16.30. Found: C, 73.49; H, 10.18%.
3
.4.5. Ethyl (E)-3-phenyl-2-propenyl ether (4a)
1
H-NMR (CDCl , 400 MHz) d 1.24 (t, Jꢂ
/
7.0 Hz,
6.0, 1.4 Hz,
15.9, 6.0 Hz, 1H), 6.60 (d, Jꢂ15.9 Hz,
7.39 (m, 5H). C-NMR (CDCl , 100 MHz)
3
3
2
1
H), 3.54 (q, Jꢂ
H), 6.29 (dt, Jꢂ
H), 7.19ꢁ
/
7.0 Hz, 2H), 4.12 (dd, Jꢂ
/
3.4.11. Ethyl (Z)-4-cyclohexyl-3-butenoate ((Z)-8b)
Compound (Z)-8b could not be isolated in pure form.
/
/
1
3
1
Partial H-NMR spectra was obtained from the mixture
/
3
1
d 15.1, 65.6, 71.1, 126.3, 126.4 (2C), 127.5, 128.5 (2C),
of (E)-8b. H-NMR (400 MHz, C D ) d 2.96 (d, Jꢂ
/7.2
6
6
1
3
3
Jꢂ
Jꢂ
32.1, 136.7.
Hz, 2H), 5.32 (dd, Jꢂ
/
11.3, 7.3 Hz, 1H), 5.58 (dt, Jꢂ
/
11.3, 7.2 Hz).
.4.6. Ethyl (E)-4-(4-methylphenyl)-3-butenoate (6a)
1
H-NMR (CDCl , 400 MHz) d 1.26 (t, Jꢂ
/
7.1 Hz,
7.1, 1.4 Hz, 2H), 4.15 (q,
15.9, 7.1 Hz, 1H), 6.44 (d,
3.4.12. Ethyl (E)-5-ethyl-3-nonenoate ((E)-8c)
3
1
H), 2.31 (s, 3H), 3.20 (dd, Jꢂ
7.1 Hz, 2H), 6.23 (dt, Jꢂ
15.9 Hz, 1H), 7.09 (d, Jꢂ
/
H-NMR (C D , 400 MHz) d 0.81ꢁ
/
0.88 (m, 6H), 0.95
1.36 (m, 8H), 1.76ꢁ1.78 (m,
7.0, 1.3 Hz, 2H), 3.93 (q, Jꢂ7.1 Hz,
2H), 5.13 (dd, Jꢂ15.3, 8.9 Hz, 1H), 5.53 (dt, Jꢂ15.3,
7.0 Hz, 1H). C-NMR (C D , 100 MHz) d 11.9, 14.2,
6
6
/
/
(t, Jꢂ
/
6.8 Hz, 3H), 1.09ꢁ
/
/
/
/
8.0 Hz, 2H), 7.25 (d, Jꢂ
/
1H), 2.88 (dd, Jꢂ
/
/
1
3
8
3
.0 Hz, 2H). C-NMR (CDCl , 100 MHz) d 14.1, 21.0,
8.4, 60.6, 120.7, 126.1 (2C), 129.1 (2C), 133.1, 134.1,
/
/
3
1
3
6
6

144
R. Takeuchi, Y. Akiyama / Journal of Organometallic Chemistry 651 (2002) 137ꢁ145
/
(1995) 1365;
(f) S.-I. Murahashi, Y. Imada, K. Nishimura, Tetrahedron 50
1
1
4.3, 23.2, 28.3, 29.8, 35.0, 38.3, 44.9, 60.2, 122.5, 138.8,
ꢀ
1
71.2. IR (neat) 1741 cm . Anal. Calc. for C H O :
1
3
24
2
(
(
1994) 453;
g) Y. Ishii, C. Gao, W.-X. Xu, M. Iwasaki, M. Hidai, J. Org.
C, 73.54; H, 11.39; O, 15.07. Found: C, 73.60; H,
1.53%.
1
Chem. 58 (1993) 6818;
h) S.-I. Murahashi, Y. Imada, Y. Taniguchi, S. Higashiura, J.
(
Org. Chem. 58 (1993) 1538;
(i) J. Kiji, T. Okano, H. Konishi, W. Nishiumi, Chem. Lett. (1989)
3
.4.13. Ethyl (Z)-5-ethyl-3-nonenoate ((Z)-8c)
1
H-NMR (C D , 400 MHz) d 0.78ꢁ
/
0.88 (m, 6H), 0.96
1.36 (m, 8H), 2.01ꢁ2.08 (m,
7.3, 1.7 Hz, 2H), 3.93 (q, Jꢂ7.1 Hz,
10.9 Hz, 1H), 5.72 (dt, Jꢂ10.9, 7.3 Hz,
H). C-NMR (C D , 100 MHz) d 11.9, 14.2, 14.3,
6
6
1
873;
j) D. Neibecker, J. Poirier, I. Tkatchenko, J. Org. Chem. 54
(1989) 2459;
k) S.-I. Murahashi, Y. Imada, Y. Taniguchi, S. Higashiura,
Tetrahedron Lett. 29 (1988) 4945;
(
t, Jꢂ
/
7.1 Hz, 3H), 1.04ꢁ
H), 2.96 (dd, Jꢂ
H), 5.12 (t, Jꢂ
/
/
(
1
2
1
2
1
/
/
(
/
/
1
3
6
6
(
(
l) J. Tsuji, K. Sato, H. Okumoto, J. Org. Chem. 49 (1984) 1341;
m) J.H. Merrifield, J.P. Godschalx, J.K. Stille, Organometallics 3
3.2, 28.7, 29.9, 33.8, 35.5, 39.5, 60.2, 121.9, 137.9,
ꢀ
1
71.1. IR (neat) 1741 cm . Anal. Calc. for C H O :
1
3
24
2
(1984) 1108;
(n) F.K. Scheffy, J.P. Godschalx, J.K. Stille, J. Am. Chem. Soc.
106 (1984) 4833;
C, 73.54; H, 11.39; O, 15.07. Found: C, 73.37; H,
1
1.57%.
(
o) J. Tsuji, J. Kiji, S. Imamura, M. Morikawa, J. Am. Chem. Soc.
6 (1964) 4350.
5] Y. Imada, O. Shibata, S.-I. Murahashi, J. Organomet. Chem. 451
8
3
.4.14. Ethyl (E)-3-nonenoate ((E)-18) [4h]
[
1
H-NMR (C D , 400 MHz) d 0.83 (t, Jꢂ
/
7.1 Hz, 3H),
1.28 (m, 6H), 1.89 (q, Jꢂ
6.9 Hz, 2H), 3.93 (q, Jꢂ7.1
15.3, 6.9 Hz, 1H), 5.59 (dt, Jꢂ
5.3, 6.9 Hz, 1H). C-NMR (C D , 100MHz) d 14.17,
(1993) 183.
[6] (a) T. Mitsudo, N. Suzuki, T. Kondo, Y. Watanabe, J. Org.
Chem. 59 (1994) 7759;
6
6
0
.94 (t, Jꢂ
/
7.1 Hz, 3H), 1.10ꢁ
/
/
6
.9 Hz, 2H), 2.88 (d, Jꢂ
/
/
(b) Y. Morisaki, T. Kondo, T. Mitsudo, Org. Lett. 2 (2000) 949.
7] (a) R. Takeuchi, N. Ue, K. Tanabe, K. Yamashita, N. Shiga, J.
Am. Chem. Soc. 123 (2001) 9525;
Hz, 2H), 5.39 (dt, Jꢂ
/
/
[
1
3
1
1
1
6
6
4.2, 22.8, 29.1, 31.6, 32.7, 38.1, 60.2, 122.5, 134.4,
ꢀ
(b) R. Takeuchi, K. Tanabe, Angew. Chem. Int. Ed. Engl. 39
(2000) 1975;
1
71.3. IR (neat) 1741 cm
.
(
(
(
(
c) R. Takeuchi, Polyhedron 19 (2000) 557;
d) R. Takeuchi, N. Shiga, Org. Lett. 1 (1999) 265;
e) R. Takeuchi, M. Kashio, J. Am. Chem. Soc. 120 (1998) 8647;
f) R. Takeuchi, M. Kashio, Angew. Chem. Int. Ed. Engl. 36
3
.4.15. Ethyl (Z)-3-nonenoate ((Z)-18) [4h]
Compound (Z)-18 could not be isolated in pure form.
1
Partial H-NMR spectra was obtained from the mixture
(1997) 263.
8] (a) T. Shibata, K. Yamashita, H. Ishida, K. Takagi, Org. Lett. 3
1
[
of (E)-18. H-NMR (400 MHz, C D ) d 2.95 (d, Jꢂ
Hz, 2H), 5.46 (dt, Jꢂ
/7.2
6
6
(
(
(
(
(
2001) 1217;
/
10.8, 7.3 Hz, 1H), 5.68 (dt, Jꢂ
/
b) T. Shibata, K. Takagi, J. Am. Chem. Soc. 122 (2000) 9852;
c) G.J. Sunley, D.J. Watson, Catal. Today 58 (2000) 293;
d) J.H. Jones, Platinum Metal Rev. 44 (2000) 94;
e) T. Ghaffar, H. Adams, P.M. Maitlis, G.J. Sunley, M.J. Baker,
1
0.8, 7.2 Hz).
A. Haynes, J. Chem. Soc. Chem. Commun. (1998) 1023;
f) M. Murakami, K. Itami, M. Ubukata, I. Tsuji, Y. Ito, J. Org.
Chem. 63 (1998) 4;
g) K. Khumtaveerporn, H. Alper, J. Org. Chem. 60 (1995) 8142;
Acknowledgements
(
This work was supported by a Grant-in-Aid for
Science Research from the Ministry of Education,
Culture, Sports, Science and Technology, Japan.
(
(h) N. Chatani, S. Yamaguchi, Y. Fukumoto, S. Murai,
Organometallics 14 (1995) 4418;
(
(
i) N. Chatani, S. Ikeda, K. Ohe, S. Murai, J. Am. Chem. Soc. 114
1992) 9710.
[
9] Palladium complex-catalyzed carbonylation of phenyl iodide in
the presence of tert-BuOH did not give the corresponding ester,
see: F. Ozawa, N. Kawasaki, H. Okamoto, T. Yamamoto, A.
Yamamoto, Organometallics 6 (1987) 1640.
References
[
1] L.S. Hegedus, Transition Metals in the Synthesis of Complex
Organic Molecules, 2nd ed., University Science Books, Mill
Valley, 1999, p. 245.
[10] (a) R.H. Crabtree, The Organometallic Chemistry of the Transi-
tion Metals, 3rd ed., Wiley, New York, 2001, p. 121;
[
2] W. Oppolzer, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 12, Pergamon
Press, Oxford, 1995, p. 905.
(b) J.P. Collman, L.S. Hegedus, J.R. Norton, R.G. Finke,
Principles and Applications of Organotransition Metal Chemis-
try, University Science Books, Mill Valley, 1987, p. 175.
[
[
3] H.M. Colquhoun, D.J. Thompson, M.V. Twigg, Carbonylation,
Plenum Press, New York, 1991.
[11] There is another possibility that oxidative addition proceeds via
N
S 2? type process, see: P.A. Evans, J.D. Nelson, J. Am. Chem.
Soc. 120 (1998) 5581.
4] (a) Y. Imada, M. Fujii, Y. Kubota, S.-I. Murahashi, Tetrahedron
Lett. 38 (1997) 8227;
[12] syn p-Allyl palladium complex is more stable than anti p-allyl
palladium complex, see: (a) J.W. Faller, M.E. Thomsen, M.J.
Mattina, J. Am. Chem. Soc. 93 (1971) 2642;
(
b) T. Satoh, M. Ikeda, Y. Kushino, M. Miura, M. Nomura, J.
Org. Chem. 62 (1997) 2662;
c) M. Sakamoto, I. Shimizu, A. Yamamoto, Bull. Chem. Soc.
Jpn. 69 (1996) 1065;
˚
(b) M. Sj o¨ gren, S. Hansson, P. Norrby, B. Akermark, M.E.
Cucciolito, A. Vitagliano, Organometallics 11 (1992) 3954;
(
˚
(c) B. Akermark, S. Hansson, A. Vitagliano, J. Am. Chem. Soc.
112 (1990) 4587.
(
(
d) A. Yamamoto, Bull. Chem. Soc. Jpn. 68 (1995) 433;
e) K. Yasui, K. Fugami, S. Tanaka, Y. Tamaru, J. Org. Chem. 60

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[
13] Based on these results, the reviewer suggested that the insertion of
carbon monoxide is the rate-determining step. It is well known
that the rate of insertion is decelerated by electron-withdrawing
[14] R.H. Crabtree, J.M. Quirk, H. Felkin, T. Fillebeen-Khan, Synth.
React. Inorg. Met. Org. Chem. 12 (1987) 407.
[15] J.L. Herde, J.C. Lambert, C.V. Senoff, Inorg. Synth. 15 (1974) 19.
[16] T.G. Schenck, J.M. Downs, C.R.C. Milne, P. Mackenzie, H.
Boucher, J. Whelan, B. Bosnich, Inorg. Chem. 24 (1985) 2334.
3
group. CF -group on the aromatic ring decreased the yield of the
product (Eq. (3)). This substituent effect also supports the
suggestion. We thank the reviewer for this useful suggestion.
For the effect of the electron-withdrawing substituent on insertion
of carbon monoxide, see: P.E. Garrou, R.F. Heck, J. Am. Chem.
Soc. 98 (1976) 4115.
[17] (Z)-Selective Honerꢁ
/
WadsworthꢁEmmons reaction, see: (a) K.
/
Ando, J. Org. Chem. 62 (1997) 1934;
(b) K. Ando, T. Oishi, M. Hirama, H. Ohno, T. Ibuka, J. Org.
Chem. 65 (2000) 4745.