Synthesis of selenol esters: Palladium-catalyzed coupling of phenyl tributylstannyl selenide with aryl iodides and carbon monoxide

Article abstract of DOI:10.1016/S0040-4039(02)00048-5

It was found that palladium complex catalyzed three-component coupling of phenyl tributylstannyl selenide with aryl iodides and carbon monoxide to afford the corresponding selenol esters in moderate to good yields.

Full text of DOI:10.1016/S0040-4039(02)00048-5

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 43 (2002) 1507–1509
Synthesis of selenol esters: palladium-catalyzed
coupling of phenyl tributylstannyl selenide with aryl iodides
and carbon monoxide
Yutaka Nishiyama,* Keiji Tokunaga, Hiroaki Kawamatsu and Noboru Sonoda*
Department of Applied Chemistry, Faculty of Engineering, Kansai University, 3-3-35 Yamate Chou Suita,
Osaka 564-8680, Japan
Received 21 November 2001; revised 27 December 2001; accepted 28 December 2001
Abstract—It was found that palladium complex catalyzed three-component coupling of phenyl tributylstannyl selenide with aryl
iodides and carbon monoxide to afford the corresponding selenol esters in moderate to good yields. © 2002 Elsevier Science Ltd.
All rights reserved.
The development of a convenient and efficient method
for the synthesis of selenol esters has attracted consider-
able attention because they are useful transfer reagents
for acyl or aroyl groups onto the various organic
coupling reaction of 1 with aryl iodides and carbon
11,12
monoxide under neutral conditions (Scheme 1).
When phenyl tributylstannyl selenide (1) was allowed to
react with iodobenzene (2) in the presence of a catalytic
amount of Pd(PPh3)4 in toluene solution under the
pressure of carbon monoxide (5 atm) at 80°C for 5 h,
Se-phenyl selenobenzoate (3), in which 1 was coupled
with 2 and carbon monoxide, was formed in 89% yield
1
–3
compounds. Although various synthetic methods of
8
selenol esters have been reported, there are some dis-
advantages: (i) handling of organoselenium compounds
which are unstable in air and moisture; (ii) difficulty of
preparation of organoselenium compounds; (iii) the
utilization of acid chlorides which are easily hydrolyzed
by water, and (iv) strongly basic or acidic reaction
conditions.
15
(entry 1 in Table 1). For the reaction at a lower
reaction temperature (50°C), the yield of 3 was slightly
decreased (entry 2). A pressure decrease of carbon
monoxide led to a decrease in the yield of 3 due to the
formation of diphenyl selenide as a by-product (entry
3). For this reaction, the chloro- and bromobenzenes
did not give 3 under the same reaction conditions as
that of 2. Table 1 shows the results of the palladium-
catalyzed synthesis of various selenol esters by the
reaction of 1 with aryl iodides and carbon monoxide.
The reaction proceeded well even when m- and p-iodo-
toluene and p-iodoanisole were used as the aryl iodides
giving the corresponding selenol esters in 67, 73 and
We have recently reported that the coupling reaction of
phenyl tributylstannyl selenide, PhSeSnBu (1), which is
3
a stable reagent in air and moisture, with aryl and alkyl
halides in the presence of palladium catalyst efficiently
proceeded under neutral condition to give the corre-
sponding diorganyl selenides in moderate to good
9
,10
yields.
In the course of our study on the utilization
of 1 in organic synthesis, we have developed the syn-
thetic method of selenol esters using a three-component
SeSnBu3
I
X
cat.
Pd(PPh3)
4
Se
+
CO
+
X
O
1
Scheme 1.
*
0
Corresponding authors. Tel.: 81-6-6368-1121; fax: 81-6-6339-4026; e-mail: nishiya@ipcku.kansai-u.ac.jp
040-4039/02/$ - see front matter © 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(02)00048-5

1
508
Y. Nishiyama et al. / Tetrahedron Letters 43 (2002) 1507–1509
a
Table 1. Synthesis of various selenol esters
Yield / %b)
Entry
Aryl Iodide
I
Selenol Ester
1
Se
O
89
3
3
2
2
2c)
66
3d)
55e)
2
3
X
Se
O
I
X
4f)
5
X = o-CH3
= m-CH3
= p-CH3
57
67
73
70
6
7
= p-CH O
3
8
= p-Cl
85
41
9g)
= p-NO2
10
Se
O
68
I
S
S
a) Reaction conditions: aryl iodide (0.25 mmol), 1 (0.25 mmol),
Pd(PPh ) (5 mol%), CO (5 atm) and toluene (2 mL) at 80 ºC for 5 h.
3
4
b) GC yields. c) At 50 ºC. d) CO (1 atm). e) PhSePh (20 %) was
formed. f) CO (50 atm). g) CO (50 atm).
7
0% yields, respectively (entries 5–7). However, for the
lytic reaction pathways involving aroyl palladium inter-
mediate (5), which is one of the active species in this
coupling reaction, was proposed. The first step involves
the oxidative addition of the aryl iodide to the low-
valent palladium species, followed by the insertion of
carbon monoxide into the palladium-carbon to form
the aroyl palladium complex (5). The following ligand
sterically congested substrate such as o-iodotoluene, the
yield of selenol ester was slightly decreased (entry 4).
For the reaction of p-chloroiodobenzene, the chloro
group remained unchanged during the coupling process
(
entry 8). When 1 was allowed to react with p-
nitroiodobenzene under the same reaction conditions as
that of the iodobenzene, the yield was low. However,
the yield was improved by the higher carbon monoxide
exchange of 5 with PhSeSnBu generates the intermedi-
3
ate 6. The subsequent reductive elimination from 6
affords the selenol ester and regenerates the low-valent
palladium species.
(
50 atm) pressure (entry 9). Se-Phenyl 2-thiophenese-
lenobenzoate was also obtained by the reaction of 1
with 2-iodothiophene and carbon monoxide in 68%
yield (entry 10).
Ar
I
COAr
I
COAr
SePh
6
L2Pd
4
L2Pd
L2Pd
We have already shown that palladium complexes such
as Pd(PPh ) act as a catalyst for the coupling reaction
3
4
5
of aryl and alkyl halides with PhSeSnBu (1) giving the
3
corresponding diorganyl selenides in moderate to good
yields under mild conditions. It has been known that
In summary, we succeeded in the synthesis of a selenol
9
ester by the reaction of PhSeSnBu with aryl iodide and
3
the aryl palladium complex (4) is easily converted to the
carbon monoxide. Further investigation on the utiliza-
tion of PhSeSnBu3 in organic synthesis is now in
progress.
aroyl palladium complex (5) under an atmosphere of
1
6,17
carbon monoxide.
Based on these results, the cata-

Y. Nishiyama et al. / Tetrahedron Letters 43 (2002) 1507–1509
1509
Acknowledgements
P. V. Mendeleev Commun. 2000, 127, including references
cited therein.
9. Nishiyama, Y.; Tokunaga, K.; Sonoda, N. Org. Lett.
This research was supported in part by a Grant-in Aid
for Scientific Research on Priority Area from the Min-
istry of Education, Science and Culture, Japan.
1999, 1, 1725.
1
0. At the same time, Beletskya showed the synthesis of
unsymmetrical selenides by the palladium-catalyzed cou-
pling of aryl halides with PhSeSnBu . See: Beletskaya, I.
3
P.; Sigeer, A. P.; Peregudov, A. P.; Petrovskii, P. V. J.
Organomet. Chem. 2000, 605, 96.
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