Mechanistic studies on Pd-catalyzed telomerization and co-cyclization of butadiene: Amphiphilicity of bis-π-allylpalladium intermediate in the presence of phosphine ligand

Article abstract of DOI:10.1246/bcsj.74.1939

Pd-catalyzed reactions of butadiene, which proceed through a bis-π-allylpalladium intermediate, (η³,η³-C₈H₁₂)Pd (2), were performed in the presence of both a pronucleophile (aceto- or cyanoacetate) and an electrophile (benzaldehyde). Methyl aceto- or cyanoacetate and benzaldehyde reacted independently with 2 to give telomers 8 and the divinylsubstituted pyranes 9, respectively. In the case of methyl cyanoacetate, the co-cyclization of 2 with 2-cyano-3-phenylpropenoate (11) formed in situ also took place to afford the cyclohexane derivative 10. Namely, three kinds of amphiphilic additions of the C₈-chain of 2 occurred to ^δ+H-Nu^δ-, ^δ+C=C^δ- and ^δ+C=O^δ- simultaneously in a one-pot reaction The Pd-catalyzed reaction of allyl chloride, allyltributylstannane, methyl cyanoacetate, and benzaldehyde was undertaken under neutral conditions, expecting the amphiphilic reactions by the intermediacy of (η³-C₃H₅)₂Pd (6) formed in situ. Allylation of both benzaldehyde and methyl cyanoacetate took place. Competitively amphiphilic bis-allylation of the polar double bond of 11 also occurred to form the 1,7-octadiene derivative 18. The mechanisms of both reactions can be explainable in terms of the amphiphilicity of the intermediates (2 and 6) in the presence of a phosphine ligand.

Full text of DOI:10.1246/bcsj.74.1939

c. Jpn.
© 2001 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 74, 1939–1945 (2001) 1939
e Chemical
ciety of Ja-
n
e Chemical
ciety of Ja-
n
Mechanistic Studies on Pd-Catalyzed Telomerization and Co-Cyclization
of Butadiene: Amphiphilicity of Bis-π-allylpalladium Intermediate in the
Presence of Phosphine Ligand
Pd-Catalyzed Reaction of Butadiene
J. Kiji et al.
01
39
Jitsuo Kiji,* Tamon Okano, Takaaki Nomura, Kayoko Saiki,† Torei Sai,† and Jiro Tsuji††,#
45
Department of Materials Science, Tottori University, Koyama, Tottori 680-8552
†Kobe Pharmaceutical University, Motoyama-Kita, Kobe 658-8558
SJA8
09-2673
109
††Department of Chemical Technology, Kurashiki University of Science and the Arts,
Tsurajima-cho, Kurashiki, Okayama 712-8012
01
(Received March 28, 2001)
01
.1
Pd-catalyzed reactions of butadiene, which proceed through a bis-π-allylpalladium intermediate, (η3,η3-C8H12)Pd
(2), were performed in the presence of both a pronucleophile (aceto- or cyanoacetate) and an electrophile (benzalde-
hyde). Methyl aceto- or cyanoacetate and benzaldehyde reacted independently with 2 to give telomers 8 and the divinyl-
substituted pyranes 9, respectively. In the case of methyl cyanoacetate, the co-cyclization of 2 with 2-cyano-3-phenyl-
propenoate (11) formed in situ also took place to afford the cyclohexane derivative 10. Namely, three kinds of am-
phiphilic additions of the C8-chain of 2 occurred to δ+H–Nuδ− δ+CwCδ−, and δ+CwOδ− simultaneously in a one-pot reac-
,
tion. The Pd-catalyzed reaction of allyl chloride, allyltributylstannane, methyl cyanoacetate, and benzaldehyde was un-
dertaken under neutral conditions, expecting the amphiphilic reactions by the intermediacy of (η3-C3H5)2Pd (6) formed
in situ. Allylation of both benzaldehyde and methyl cyanoacetate took place. Competitively amphiphilic bis-allylation
of the polar double bond of 11 also occurred to form the 1,7-octadiene derivative 18. The mechanisms of both reactions
can be explainable in terms of the amphiphilicity of the intermediates (2 and 6) in the presence of a phosphine ligand.
Ligand-modified palladium complexes are the most versa-
tile catalysts for C–C bond formations.1,2 Among them, the
catalytic allylation of pronucleophiles (HNu) (Chart 1),3,4 and
telomerization (Chart 2, route a)5–10 and co-cyclization (Chart
2, route b)11–15 of butadiene are the typical reactions. These re-
actions proceed via π-allylpalladium intermediates 1 and 2.
In the reaction of Chart 1, it is important to notice that π-al-
lylpalladium halide 1 reacts with soft carbon nucleophiles,16
while other allylmetals, such as allylmagnesium and -nickel,
react with electrophiles, e.g., aldehydes. Therefore, the reac-
tion pathway of the intermediate 1 is in marked contrast to that
of other allyl metals. The Pd-catalyzed allylation of pronu-
cleophiles takes place smoothly under basic conditions with a
variety of allylic compounds, such as halides and esters. On
the other hand, allylation with allyl carbonates,17 vinylox-
iranes,18,19 and acetates20 occurs even under neutral conditions.
The Pd-catalyzed reactions of butadiene (Chart 2) are differ-
ent from those catalyzed by nickel catalysts.21 Unlike nickel
catalysts, neither cyclodimerization nor trimerization to form
cyclooctadiene or cyclododecatriene, respectively, takes place
with palladium catalysts. Palladium complexes catalyze two
important reactions of butadiene. One is linear dimerization
with the incorporation of pronucleophiles, namely the telomer-
ization to form 3 (Chart 2, a route), which proceeds readily un-
der neutral conditions. The other reaction is co-cyclization
with CwO or CwN bonds to form the six-membered heterocy-
clic compounds 4 with two vinyl groups (Chart 2, b route).
For example, co-cyclization with aldehydes affords divinyltet-
rahydropyranes. This co-cyclization was reported in the early
1970’s,11–15 soon after discovering the telomerization of buta-
diene with pronucleophiles, such as active methylene com-
pounds.
The formation of 3 and 4 is quite interesting, because the re-
action pathways of bis(π- allyl)palladium intermediate 2 are in
contrast to that of 1, which reacts only with nucleophiles. It
should be recognized that 2 can react with both electrophiles
(aldehydes) as well as nucleophiles. Yamamoto and co-
workers22 reported on the amphiphilic nature of a simple bis(π-
allyl)palladium (6), which is formed in situ from 1 and allyl-
tributylstannane (5) (Chart 3). Recently, the application of the
amphiphilic reaction to the synthesis of medium-sized car-
bocycles has also been reported.23 They have shown that one
allyl group reacts with a nucleophile, and the other with an
electrophile. Consequently, there is a possibility that one allyl
unit of 2 reacts with a nucleophile, and the other with an elec-
trophile independently of each other to form 7, as shown in
Chart 4(a route).
To obtain a consistent mechanistic explanation concerning
the reaction of the π-allylpalladium intermediates 1, 2, and 6,
we attempted a Pd-catalyzed reaction of butadiene, which pro-
ceeds via intermediate 2, in the presence of both electrophiles
# Tokyo Institute of Technology, Emeritus. Present address: 602-
128 Tsu, Kamakura, Kanagawa 248-0032, Japan
and pronucleophiles. In addition, this paper considers the al-
lylation of pronucleophiles through 6.

1940 Bull. Chem. Soc. Jpn., 74, No. 10 (2001)
Pd-Catalyzed Reaction of Butadiene
Chart 1.
Chart 2.
Chart 3.
Chart 4.
4-vinyl-1- cyclohexene) were formed in all cases. Their yields
are not included in Table 1. The yields of 8, 9, and 10 varied
from reaction to reaction. However, three kinds of products (8,
9, and 10) were always formed when both benzaldehyde and
methyl cyanoacetate were present in the reaction system. The
expected product 7 was not formed even in the presence of tri-
ethylamine or DBU. When methyl acetoacetate was used in-
stead of cyanoacetate, the cyclic product 10 was not formed.
The formation of 10 can be explained by the following reac-
tion pathway. Firstly, 2-cyano-3-phenylpropenoate (11) is
formed in situ by aldol condensation of methyl cyanoacetate
with benzaldehyde, followed by dehydration (Chart 5). This
polar olefin then undergoes double allylation in a similar man-
ner as the co-cyclization with benzaldehyde. There are only
few examples of the co-cyclization of 2 with CwC double
bonds,23 though extensive work on reactions of this type has
been done using nickel catalysts.21
Results and Discussion
Catalytic Reaction of Butadiene in the Presence of Alde-
hyde and Aceto- or Cyanoacetate. The reaction of butadi-
ene in the presence of both benzaldehyde and methyl aceto- or
cyanoacetate was studied with the expectation that the one al-
lyl unit of the C8-Pd intermediate 2 reacts with methyl aceto-
or cyanoacetate and the other with benzaldehyde to form 7
(Chart 4a). Palladium(Ⅱ) acetate combined with triphen-
ylphosphine was used as the catalyst.
Gas chromatography/mass spectrometry (GC/MS) of the re-
action mixture revealed that a variety of compounds were
formed. However, the expected product 7 was not obtained at
all. Instead, methyl aceto- or cyanoacetate and benzaldehyde
reacted independently to give telomers 8 and pyranes 9, re-
spectively. In addition, the cyclohexane derivatives 10 were
obtained. All of these products (8, 9, and 10) were a mixture
of their isomers. Two isomers of 10 were detected by GC.24
The results are summarized in Table 1. All of the experiments
were performed in the presence of an excess amount of butadi-
ene. Therefore, the dimers of butadiene (1,3,7-octatriene and
In the reactions of butadiene described above, the catalyst
containing the phosphine ligand seems to be a favorable
choice. In the presence of the phosphine ligand, however, 2 is
converted into a σ-allyl-π-allylpalladium intermediate 12.

J. Kiji et al.
Bull. Chem. Soc. Jpn., 74, No. 10 (2001) 1941
Table 1. Reaction of Butadiene with Benzaldehyde and Pronucleophiles (HNu) in One-Pot (Chart 4)a)
PhCHO
mmol
20
—
20
10
10
20
20
HNu
E, mmol
—
CN, 20
CN, 20
CN, 10
CN, 10
CH3CO, 20
CH3CO, 20
CH3CO, 20
Temp
°C
80
80
80
80
reflux
80
80
reflux
Yield/%
9
86
—
73
48
33
54
44
Pd(OAc)2/PPh3
Solvent
8
10
—
—
6
30
24
—
—
—
1/2
1/2
1/2
1/6
1/6
1/2
1/4
1/2
i-PrOH
i-PrOH
i-PrOH
i-PrOH
THF
i-PrOH
i-PrOH
THF
—
95
63
25
15
89
93
82
20
16
a) butadiene, 10 mL; solvent, 5 mL; Pd(OAc)2, 0.5 mmol; time, 20 h.
Chart 5.
Chart 6.
Chart 7.
Complex 12 was isolated and its reaction with cyanoacetate
was studied in detail by Jolly and co-workers using NMR
spectoscopy.25 According to their results, the first step of the
telomerization with cyanoacetate is abstraction of the proton
from the cyanoacetate by one of the nucleophilic allyl units,
while the other allyl unit remains as a π-allyl form 13. Then,
the electrophilic addition of the π-allyl unit to the coordinated
soft carbon nucleophile affords the telomers 8 (Chart 6). In
this way, even in the absence of a base, proton abstraction from
pronucleophile occurs by one of the allyl units of the C8-Pd in-
termediate. This explanation indicates that one of the allyl
units acts as a base, in other words, as a nucleophile, and the
other as an electrophile. That is to say, in the presence of the
phosphine ligand, intermediate 2 is converted into 12, which
then shows amphiphilic reactivity.
Co-cyclization with benzaldehyde is explained by double al-
lylation of the CwO double bond with amphiphilic 2 after con-
version into 12 in the presence of phosphine ligand. Namely,
while π-allylpalladium 1, even in the presence of triphen-
ylphosphine, does not attack the positive carbon atom of the
carbonyl group at all, the one allyl unit of 2 attacks the positive
carbon atom and the other the negative oxygen atom to form 9
(Chart 7).
Reaction of Allyl Chloride, Allyltributylstannane, Meth-
yl Cyanoacetate, and Benzaldehyde in One-Pot. The sim-
plest member of the bis(π-allyl)palladium system is (η3-
C3H5)2Pd (6). A traditional synthetic method of 6 is the reac-
tion of 1 with allylmagnesium halide at low temperature.25–27
Yamamoto and co-workers28 have shown that 6 is also formed
by the reaction of 1 with allyltributylstannane (5). Following

1942 Bull. Chem. Soc. Jpn., 74, No. 10 (2001)
Pd-Catalyzed Reaction of Butadiene
their method (Chart 3), we prepared bis(π-allyl)palladium (6)
in situ and allowed it to react with methyl cyanoacetate in the
presence of triphenylphosphine (Chart 8).
duced to a zero-valent species. π-Allylpalladium chloride (1)
is formed by the oxidative addition of allyl chloride to the
Pd(0) complex and gives 6 in the presence of allyltributylstan-
nane. In this way, if allyl chloride and allyltributylstannane are
still present in the reaction solution, 6 is regenerated; thus, the
catalytic reaction is possible.
Then, the reaction of allyl chloride, allyltributylstannane,
methyl cyanoacetate, and benzaldehyde was undertaken in the
presence of a catalytic amount of Pd(OAc)2 and triphenylphos-
phine, expecting the amphiphilic reactions of 6 formed in situ
with the liberation of tributylchlorostannane (Chart 9).
The reaction mixture was hydrolyzed and analyzed by GC.
The products were homoallylic alcohol 17 and the allylated
product 16 of cyanoacetate and 1,2-diallylated product 18 of
the polar olefin formed from cyanoacetate and benzaldehyde.
The results are given in Table 3. The formation of the diallyl-
ated product (18) has already been discussed as the am-
phiphilic reaction of bis-π-allylpalladium 6 by Yamamoto et
al.22
Allylated products (15 and 16) were formed (Table 2).
Without the phosphine ligand, allylation did not occur. Neither
1 nor allyltributylstannane (5) by itself reacted with methyl cy-
anoacetate. Consequently, the formation of allylated products
means the intermediacy of bis(π-allyl)palladium formed in
situ. The reaction of Chart 8 can be explained as follows. The
coordinating and basic alkoxide anion of π-allyl(homoallyl-
oxy)palladium, the same type of intermediate as 14 formed by
the reaction of 6 with benzaldehyde, deprotonates methyl cy-
anoacetate to form the homoallyl alcohol 17, while the remain-
ing allyl group reacts as an electrophile with carboanion to
form 15 and/or 16. The formation of the homoallyl alcohol 17
is in contrast to that of the pyranes 9 in the reaction of butadi-
ene (Chart 4), where the alkoxide anion of the intermediate 14
reacts with the remaining allyl unit before deprotonation by re-
ductive elimination.
In this stoichiometric reaction of Chart 8, palladium was re-
When either allyl chloride or allyltributylstannane was ab-
sent, the allylations did not occur at all. In contrast to the reac-
tion of butadiene, the co-cyclization-type reaction, namely the
addition of the two allyl units of 6 to both carbon and oxygen
atoms of benzaldehyde to afford an allylic ether 19 did not take
place. According to a mechanistic study done byYamamoto,28
the formation of homoallylic alcohol 17 proceeds via a π-al-
lyl(homoallyloxy)palladium intermediate, which reacts with
allyltributylstannane to regenerate 6 along with the liberation
of the alkoxystannane. This is the reason why allylic ether 19
is not formed.
Table 2. Stoichiometric Reaction of (η3-C3H5)2Pd Formed
in situ with Benzaldehyde and Methyl Cyanoacetate
(Chart 8)a)
CNCH2COOCH3
PhCHO
mmol
—
1.0
0.5
Temp
°C
−20
−20
−40
Yield/%
15 16 17
22 12
mmol
1.0
—
—
22
—
—
—
58 30
0.5
a) (η3-C3H5PdCl)2/C3H5SnBu3/PPh3
(mmol); solvent, THF 30 mL.
=
0.5/1.0/2.0
In this catalytic reaction it is evident that the one allyl unit
Chart 8.
Chart 9.

J. Kiji et al.
Bull. Chem. Soc. Jpn., 74, No. 10 (2001) 1943
Table 3. Reaction of Allyl Chloride, Allylstannane, Cyanoacetate, and Benzaldehyde(Chart 9)a)
CNCH2COOCH3
PhCHO
Temp
Yield/%b)
Solvent
mmol
1.1
mmol
1.0
mmol
—
0.4
1.3
1.1
mmol
0.5
—
1.0
1.0
°C
100
100
100
reflux
16
—
86
17
21
—
18
—
—
DMSO
DMSO
DMSO
THF
0.8
0.7
1.6
1.6
24 trace 47
64 trace
1.7
1.9
5
a) Pd(OAc)2/2 PPh3, 0.1/0.2 mmol; time, 20 h
b) Based on benzaldehyde.
Chart 10.
Chart 11.
of 6 formed in the catalytic cycle acts as a nucleophile ab-
stracting the proton from the cyanoacetate in a similar manner
to that of the C8-Pd intermediate. This explanation means that
propene should be evolved during allylation. At 100 °C, pro-
pene is too volatile to be detected. Therefore, to confirm the
role of the allyl group as the nucleophile, cinnamyl chloride
was used instead of allyl chloride, expecting the formation of
the intermediate 20 (Chart 10). If the cinnamyl group of 20
acts as the nucleophile in this case, phenylpropenes 22 must be
formed. Thus, a one-pot reaction of cinnamyl chloride, allyl-
tributylstannane, and methyl cyanoacetate was carried out at
100 °C in the presence of a catalytic amount of Pd(OAc)2/PPh3
(Chart 11).
Since cinnamyl chloride readily forms a cross-coupling
product with allyltributylstannane, 1-phenyl-1,5-hexadiene
(21) was formed in 68% yield.29 In this reaction, however,
phenylpropenes 22, which were formed from the cinnamyl
group as a result of proton abstraction, were detected by GC/
MS together with allylated products 15, 16, and 23. Compared
with the other products, phenylpropenes were still so volatile
that their yields were not determined.
bound to the one end and the nucleophile to the other end of
the C8-chain, was not formed. Instead, benzaldehyde and me-
thyl cyanoacetate underwent amphiphilic reactions with buta-
diene separately. In parallel with the reaction of butadiene,
mixtures of allyl chloride, allyltributylstannane, benzaldehyde,
and methyl cyanoacetate were allowed to react in a one-pot
manner (Chart 9). In this case, allylated products of cyanoace-
tate and benzaldehyde were formed. The formations of the
products of both reactions, except for homoallylic alcohol 17,
are explained by the amphiphilic allylation through the bis(π-
allyl)palladium intermediates (2 and 6) in the presence of the
phosphine ligand. As described above, bis(π-allyl)palladium
complexes 2 and 6 have a π-allyl-σ-allyl structure in the pres-
ence of the phosphine ligand. However, for simplicity and in
order to emphasize their amphiphilic reactivity in consistent
mechanistic explanations, we use here the bis-π-allyl struc-
tures as adopted for elucidating reaction paths everywhere.
Thus, the Pd-catalyzed allylation of pronucleophiles (so-called
Tsuji–Trost reaction) under neutral conditions and the reaction
of butadiene are schematically expressed as in Scheme 1. It is
worth noting that the three kinds of amphiphilic reactions of 2
(Chart 4) take place simultaneously in a one-pot manner.
Conclusion
Experimental
A palladium-catalyzed three-component reaction of butadi-
ene, aldehyde (electrophile) and methyl aceto- or cyanoacetate
(pronucleophile) (Chart 4) was attempted in the absence of a
base; but the expected product 7, in which the electrophile is
General. Solvents were purified by conventional methods
and used under an atmosphere of argon. Liquefied butadiene was
dried over Molecular Sieve 3A at room temperature. Other com-

1944 Bull. Chem. Soc. Jpn., 74, No. 10 (2001)
Pd-Catalyzed Reaction of Butadiene
Scheme 1. Amphiphilic reactions of bis(π-allyl)palladium.
mercially available reagents were used without further purifica-
tion. A gas-chromatographic analysis was performed on a Shi-
madzu GC-14B (TCD). Spectral data were recorded by the fol-
lowing instruments: IR, Perkin Elmer 1600FT-IR; NMR, JEOL
GX-200 and Varian VXR-500 (500 MHz); GC/MS, Hitachi M-
4100 MS/MS system.
Allyltributylstannane (5), Methyl Cyanoacetate, and Benzal-
dehyde (Chart 8). A typical example is the following. Com-
plex 1 (0.5 mmol) was placed in a two-neck flask. The atmo-
sphere was replaced with argon and THF (30 mL) was added. Af-
ter the solution was cooled to ca. −60 °C, a THF solution of allyl-
tributylstannane (1 mmol) was added. The solution was stirred
between −60 and −40 °C for 1 h. Triphenylphosphine (2 mmol),
methyl cyanoacetate (0.5 mmol), and benzaldehyde (0.5 mmol)
were added in this order at −40 °C. While the flask was left in the
bath with stirring overnight, the temperature was gradually raised
to room temperature. The solution was treated with water. The
products were extracted with ether and distilled under reduced
pressure. The yields were determined by GC (column, Silicon
DC-560, 3 m, at programmed temperature ranging from 100 to
250 °C at a rate of 5 °C/min) using 4-methylbiphenyl as an inter-
nal standard. Identification of the products was done by GC-MS;
their retention times were compared with those of authentic sam-
ples prepared by the reported method.17b The results are given in
Table 2.
Reaction of Allyl Chloride, Allyltributylstannane, Methyl
Cyanoacetate, and Benzaldehyde (Chart 9). The following is
a representative example. In a two-neck flask equipped with a
condenser, Pd(OAc)2 (0.10 mmol), triphenylphosphine (0.20
mmol), and a stirring bar were placed. The atmosphere was re-
placed with argon. THF (10 mL), allyl chloride (1.7 mmol), allyl-
stannane 5 (1.9 mmol), methyl cyanoacetate (1.1 mmol), and ben-
zaldehyde (1.0 mmol) were added by syringe in this order under
an argon atmosphere. The solution was heated at 100 °C for 20 h.
The isolation and analysis of the products were done as described
above. The results are summarized in Table 3.
Reaction of Butadiene, Methyl Cyanoacetate, and Benzal-
dehyde (Chart 4). The typical procedure was as follows. In a
50 mL stainless steel autoclave, Pd(OAc)2 (0.5 mmol), triphen-
ylphosphine (1.0 mmol), and a stirring bar were placed. Then, 2-
propanol (5 mL), methyl cyanoacetate (20 mmol), and benzalde-
hyde (20 mmol) were added by a syringe under an atmosphere of
argon. The autoclave was cooled in a dry ice-methanol bath. Liq-
uefied butadiene (10 mL) was added by syringe. The autoclave
was stirred magnetically at 80 °C for 20 h. After the reaction, the
solvent was removed by a rotary evaporator and the residue was
distilled by a glass tube oven (Shibata GTO-350RD) under re-
duced pressure. The products were analyzed by GC using o-ter-
phenyl as an internal standard (column, Silicon DC-560, 3 m, 250
°C). The yields were calculated by assuming that the peak area ra-
tio of the products to that of o-terphenyl corresponds to the ratio of
their weights. Identification of the products was done by GC/MS
1
and H NMR spectroscopy. The reaction conditions and the re-
sults are given in Table 1.
One of the isomers of 10, which was eluted earlier in GC, was
isolated by recycle HPLC (column, JA1GEL 1H+2H; eluent,
CHCl3 of a rate of 3.5 mL/min).30 IR (neat film) 2242 (ν CwN),
1744 (νCwO); 1H NMR (500 MHz, CDCl3) δ 1.53 (m, 1H), 1.91 (m,
2H), 2.04 (m, 1H), 2.83 (m, 2H), 2.98 (d, J = 12 Hz, 1H), 3.44 (s,
3H), 4.83 (d, J = 10.5 Hz, 1H), 4.95 (d, J = 12 Hz, 1H), 5.13 (d, J
= 10.5 Hz, 1H), 5.17 (d, J = 17 Hz, 1H), 5.40 (m, 1H), 5.78 (m,
1H), 7.26 (m, 5H); 13C NMR (CDCl3) δ 27,7, 31.6, 41.4, 48.6,
52.7, 53.8, 59.0, 115.0, 116.8, 118.4, 127.9, 128.3, 128.4, 129.0,
136.4, 137.2, 139.6, 168.3; HRMS (EI) Calcd for C19H21NO2:
295.1573, found: 295.1575.
Reaction of Cinnamyl Chloride, Allyltributylstannane, and
Methyl Cyanoacetate (Chart 11). The reaction was performed
as described above for allyl chloride.
This work was supported by a Grant-in-Aid for Scientific
Research (C)(2) (No.09650962) from the Ministry of Educa-
Stoichiometric Reaction of π-Allylpalladium Chloride (1),

J. Kiji et al.
Bull. Chem. Soc. Jpn., 74, No. 10 (2001) 1945
16 J. Tsuji, H. Takahashi, and M. Morikawa, Tetrahedron
Lett., 1965, 4387.
17 a) J. Tsuji, Tetrahedron, 42, 4361 (1986); b) J. Tsuji, I.
Shimizu, I. Minami, Y. Ohashi, T. Sugiura, and K. Takahashi, J.
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18 J. Tsuji, H. Kataoka, and Y. Kobayashi, Tetrahedron Lett.,
22, 2575 (1981).
19 B. M. Trost and G. A. Molander, J. Am Chem. Soc., 103,
5969 (1981).
tion, Science, Sports and Culture. We thank Japan Analytical
Industry Co. Ltd., for separating the products by recycle
HPLC.
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