Phenyl tributylstannyl selenide as a promising reagent for introducion of the phenylseleno group

Article abstract of DOI:10.1021/jo026894i

A new synthetic method of organoselenium compounds has been developed. When phenyl tributylstannyl selenide (PhSeSnBu₃) was allowed to react with acyl or aroyl chlorides in the presence of a catalytic amount of a palladium complex such as Pd(PPh₃)4, Se-phenyl selenol esters were obtained in moderate to good yields. Similarly, the palladium complex catalyzed the reaction of PhSeSnBu₃ with α-halo carbonyl compounds to afford the corresponding α-phenyseleno carbonyl compounds in moderate yields.

Full text of DOI:10.1021/jo026894i

P h en yl Tr ibu tylsta n n yl Selen id e a s a P r om isin g Rea gen t for
In tr od u cion of th e P h en ylselen o Gr ou p
Yutaka Nishiyama,* Hiroaki Kawamatsu, Saori Funato, Keiji Tokunaga, and Noboru Sonoda*
Department of Applied Chemistry, Faculty of Engineering, Kansai University,
Suita, Osaka 564-8680, J apan
nishiya@ipcku.kansai-u.ac.jp
Received December 22, 2002
A new synthetic method of organoselenium compounds has been developed. When phenyl
tributylstannyl selenide (PhSeSnBu3) was allowed to react with acyl or aroyl chlorides in the
presence of a catalytic amount of a palladium complex such as Pd(PPh3)4, Se-phenyl selenol esters
were obtained in moderate to good yields. Similarly, the palladium complex catalyzed the reaction
of PhSeSnBu3 with R-halo carbonyl compounds to afford the corresponding R-phenyseleno carbonyl
compounds in moderate yields.
In tr od u ction
we found that Se-phenyl selenol esters and R-phenylse-
leno carbonyl compounds were synthesized by the pal-
ladium complex-catalyzed reaction of 1 with acid chlo-
Since Sharpless and Reich have demonstrated an
effective olefin-forming method by the use of selenoxide
elimination in the early 1970s,1 the interest in the utility
of organoselenium compounds in organic synthesis grew.
In the organic chemistry by the use of organoselenium
compounds as key intermediates, the organoselenium
compounds are often diorganyl selenides, and much effort
is being devoted to accomplish the synthesis of these
compounds.2 However, many synthetic methods some-
times suffer from the improper handling of selenium
reagents used as selenium sources because of their
instability against air and moisture and basic or acidic
reaction conditions. Thus, the development of new syn-
thetic methods using stable selenium reagents under
mild conditions would have significant synthetic value.
Transition metal complex catalyzed reactions of aryl
halides with organoheteroatom compounds having M-M′
(M and M′ ) heteroatom) bonds are now widely used for
the synthesis of various heteroatom-containing com-
pounds;3 however, similar reactions of aryl halides with
organoselenium compounds containing a selenium-het-
eroatom bond have not been reported. Our and Be-
letskaya’s groups have recently shown that the palladium
complex catalyzed the coupling reaction of phenyl tribu-
tylstannyl selenide (PhSeSnBu3) (1), which is stable
against air and moisture, with aryl halides giving the
corresponding diaryl selenides in moderate to good
yields.4 In the course of our study on the utilization of
phenyl tributylstannyl selenide, in organic reactions,5-7
(3) There are some reports on the palladium complex catalyzed
reaction of aryl and alkyl halides with organic heteroatom compounds
having heteroatom-heteroatom bonds. B-B: Ishiyama, T.; Murata,
M.; Miyaura, N. J . Org. Chem. 1995, 60, 7508. Si-Si: Matsumoto,
H.; Nagashima, S.; Yoshihiro, K.; Nagai, Y. J . Organomet. Chem. 1975,
85, C1. Matsumoto, H.; Yoshihiro, K.; Nagashima, S.; Watanabe, H.;
Nagai, Y. J . Organomet. Chem. 1977, 128, 401. Matsumoto, H.;
Nagashima, S.; Sato, T.; Nagai, Y. Angew. Chem. 1978, 17, 279. Faboru,
C.; Griffiths, R. W.; Pidcock, A. J . Organomet. Chem. 1982, 225, 331.
Nakano, T.; Takahashi, M.; Ashizawa, T.; Arai, T.; Seki, S.; Matsumoto,
H.; Nagai, Y. Chem. Lett. 1982, 613. Hiyama, T.; Obayashi, M.; Mori,
I.; Nozaki, H. J . Org. Chem. 1983, 48, 912. Hatanaka, Y. Hiyama, T.
Tetrahdron Lett. 1987, 28, 4715. Al-Si: Trost, B. M.; Yoshida, J .
Tetrahedron Lett. 1983, 24, 4895. Si-P: Tunney, S. E.; Stille, J . K. J .
Org. Chem. 1987, 52, 748. Si-Sn: Mori, M.; Kaneta, N.; Shibasaki,
M. J . Org. Chem. 1991, 56, 3487. S-Sn: Beletskaya, I. P. J .
Organomet. Chem. 1983, 250, 551. Carpita, A.; Rossi, R.; Scamuzzi,
B. Tetrahedron Lett. 1989, 30, 2699. J uxiang, C.; Crisp, G. T. Synth.
Commun. 1992, 22, 683. Sn-Sn: Farina, V.; Hauck, S. I. J . Org. Chem.
1991, 56, 4317. Kosugi, M.; Shimizu, K.; Ohtani, A.; Migita, T. Chem.
Lett. 1981, 829.
(4) (a) Nishiyama, Y.; Tokunaga, K.; Sonoda, N. Org. Lett. 1999, 1,
1725. (b) Beletskaya, I. P.; Sigeev, A. S.; Peregudov, A. S.; Petrovskii,
P. V. J . Organomet. Chem. 2000, 605, 96. (c) Beletskaya, I. P.; Sigeev,
A. S.; Peregudov, A. S.; Petrovskii, P. V. Russ. J . Org. Chem. 2001,
37, 1463.
(5) (a) Nishiyama, Y.; Aoyama, S.; Hamanaka, S. Phosphorus,
Silicon, Sulfur 1993, 65, 1245. (b) Nishiyama, Y.; Ohashi, H.; Itoh,
K.; Sonoda, N. Chem. Lett. 1998, 159. (c) Nishiyama, Y.; Tokunaga,
K.; Kawamatsu, H.; Sonoda, N. Tetrahedron Lett. 2002, 1507.
(6) Beletskaya has recently reported the utilization of phenyl
tributylstannyl selenide, which was generated in situ by the reaction
of diphenyl diselenide with hexabutyl distannane with daylight in
organic synthesis. See: (a) Bumagin, N. A.; Gulevich, Y. V.; Beletskaya,
I. P. Izv. Akad. Nauk SSSR, Ser. Khim. 1984, 953. (b) Bumagin, N.
A.; Gulevich, Y. V.; Beletskaya, I. P. J . Organomet. Chem. 1985, 285,
415. (c) Beletskaya, I. P.; Sigeev, A. S.; Peregudov, A. S.; Petrovskii,
P. V. Mendeleev Commun. 2000, 127.
(1) (a) Sharpless, K. B.; Young, M. W. J . Org. Chem. 1975, 40, 947.
(b) Reich, H. J .; Renga, J . M.; Reich, I. L. J . Org. Chem. 1974, 39,
2133.
(2) Krief, A.; Hevesi, L. In Organoselenium Chemistry; Springer-
Verlag: Berlin, 1988; Vol. 1. Paulmier, C. In Selenium Reagents and
Intermediates in Organic Synthesis; Pergamon Press: Oxford, 1986.
Patai, S.; Rappoport, Z. In The Chemistry of Organic Selenium and
Tellurium Compounds; Wiley: New York, 1986; Vols. 1 and 2. Krief,
A. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon
Press: Oxford, 1991; Vol. 3, pp 85-192 and references therein.
(7) The other applications of organoselenium compounds having a
Se-Sn bond are very few due to the lack of method for the activation
of the selenium-tin bond.8 See: (a) Shimada, K.; Okuse, S.; Takikawa,
Y. Bull. Chem. Soc. J pn. 1992, 65, 2848. (b) Segi, M.; Kojima, T.;
Nakajima, T.; Suga, S. Tetrahedron Lett. 1991, 32, 7427. (c) Segi, M.;
Kojima, T.; Nakajima, T.; Suga, S. Synlett 1991, 105. (d) Harpp, D.
N.; Gingras, M. J . Am. Chem. Soc. 1988, 110, 7737. (e) Stelius, K.;
Mrani, M. J . Am. Chem. Soc. 1982, 104, 3104. (f) Baudler, H.;
Suchomel, G.; Fuerstenberg, G.; Schings, O. Angew. Chem. 1981, 93,
1087. (g) Crosse, B. C.; Hutson, G. V. J . Chem. Soc. A 1967, 2014.
10.1021/jo026894i CCC: $25.00 © 2003 American Chemical Society
Published on Web 04/02/2003
J . Org. Chem. 2003, 68, 3599-3602
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Nishiyama et al.
TABLE 1. P a lla d iu m -Ca ta lyzed Rea ction of P h SeSn Bu 3
w ith Ar oyl or Acyl Ch lor id esa
rides and R-halo carbonyl compounds in moderate to good
yields.
Resu lts a n d Discu ssion
(1) Syn th esis of Se-P h en yl Selen ol Ester s. The
development of a convenient and efficient method for the
synthesis of Se-phenyl selenol esters has attracted con-
siderable attention9 because they are useful transfer
reagents for acyl or aroyl groups onto the various organic
compounds.10-12 Then, the synthesis of Se-phenyl selenol
esters by reaction of phenyl tributylstannyl selenide (1)
with benzoyl chloride (2a ) in the presence of a catalytic
amount of Pd(PPh3)4 was examined. When 1 was allowed
to react with 2a in the presence of a catalytic amount of
Pd(PPh3)4 at 25 °C for 6 h, Se-phenyl seleno benzoate (3a )
was formed in 97% yield (entry 1, Table 1).17 The results
of the synthesis of various Se-phenyl selenol esters by
the palladium-catalyzed coupling of 1 with aroyl or acyl
chlorides are shown in Table 1. The treatment of 1 with
p-methyl-, p-methoxy-, p-chloro-, p-nitro-, and p-cyanoben-
zoyl chloride under reaction conditions similar to those
for 2a afforded the corresponding Se-aryl selenol esters
in 71-91% yields (entries 2-6). In the reaction of 1- and
2-naphthyl acid chloride, the coupling reaction also
proceeded to give selenol esters in 87 and 92% yields,
respectively (entries 7 and 8). Similarly, the coupling
reaction of 1 with acyl chlorides having a linear alkyl
chain or benzylic group was successfully occurred, and
Se-aryl selenol esters were obtained in 92 and 85% yield
(entries 9 and 10). However, in the case of R-methyl- and
R,R-dimethyl-substituted acyl chloride, the yields of
product were slightly decreased (entries 11 and 12).
0
(8) The bond energy of the Se-Sn bond is D298 ) 98.2 ( 3 kcal/
mol. See: Ho, K. C. M. In Thermodynamic Data for Inorganic Sulfides,
Selenides, and Tellurides; Rechhood Press: England, 1974; p 594.
(9) (a) Bates, G. S.; Diakur, J .; Masamune, S. Tetrahedron Lett.
1976, 49, 4423. (b) Grieco, P. A.; Yokoyama, Y.; Williams, E. J . Org.
Chem. 1978, 43, 1283. (c) Mullen, G. P.; Luthra, N. P.; Dunlap, R. B.;
Odom, J . D. J . Org. Chem. 1985, 50, 811 and references cited therein.
(10) For recent reviews on selenol esters: (a) Ogawa, A.; Sonoda,
N. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.;
Pergamon: Oxford, 1991; Vol. 6, pp 461-484. (b) Ogawa, A.; Sonoda,
N. In Comprehensive Organic Functional Group Transformations;
Katrizky, A. R., Meth-Cohn, O., Ress, C. W., Eds.; Pergamon: Oxford,
1995; Vol. 5, pp 231-255.
(11) For leading references, see: (a) Pfenninger, J .; Heuberger, C.;
Graf, W. Helv. Chim. Acta 1980, 63, 2328. (b) Kozikowski, A. P.; Ames,
A. J . Am. Chem. Soc. 1980, 102, 860. (c) Kozikowsky, A. P.; Ames, A.
Tetrahedron 1985, 41, 4821. (d) Boger, D. L.; Roberge, K. D. J . Org.
Chem. 1988, 53, 3377. (e) Boger, D. L.; Mathvink, R. J . J . Org. Chem.
1989, 54, 1777. (f) Schwartz, C. E.; Curran, D. P. J . Am. Chem. Soc.
1990, 112, 9272. (g) Boger, D. L.; Mathvink, R. J . J . Org. Chem. 1992,
57, 1429.
a
Reaction conditions: 1 (0.25 mmol), aroyl or acyl chloride (0.25
mmol), Pd(PPh3)4 (1 mol %) and toluene (2 mL) at 25 °C for 6 h.
GC yield.
b
(12) Selenol esters can also be converted to the corresponding acids,13
esters,13 amides,13a ketones,14 aldehydes,15 and alkenyl selenides.16
(13) (a) Kozikowsky, A. P.; Ames, A. J . Org. Chem. 1978, 43, 2735.
(b) Dabdoub, M. J .; Viana, L. H. Synth. Commun. 1992, 22, 1619.
(14) (a) Back, T. G.; Kerr, R. G. Tetrahedron Lett. 1982, 23, 3241.
(b) Sviridov, A. F.; Ermolenko, M. S.; Yashusky, D. V.; Kochetkov, N.
K. Tetrahedron Lett. 1983, 24, 4355. (c) Sviridov, A. F.; Ermolenko,
M. S.; Yashusky, D. V.; Kochetkov, N. K. Tetrahedron Lett. 1983, 24,
4359.
Although a detailed study on the reaction pathway has
not yet been completed, a plausible catalytic pathway was
shown in Scheme 1. The first step involves the oxidative
addition of the aroyl chloride to the low-valent palladium
species to form an aroylpalladium chloride species (4).18,19
The following ligand exchange of 4 with PhSeSnBu3
generates the intermediate 5. The subsequent reductive
elimination from 5 affords the coupling product and
regenerate the low-valent palladium species.
(15) Kuniyasu, H.; Ogawa, A.; Higaki, K.; Sonoda, N. Organome-
tallics 1992, 11, 3937.
(16) Petasis, N. A.; Lu, S.-P. Tetrahedron Lett. 1995, 36, 2393.
(17) Beletskaya has shown the synthetic method of selenol esters
by the reaction of acyl and aroyl chloride with PhSeSnBu3, which was
generated in situ by the reaction of PhSeSePh with Bu3SnSnBu3 under
daylight conditions, in the absence of palladium catalyst. Thus, we
examined the reaction of PhSeSnBu3, which was synthesized by our
method (see the Experimental Section), and benzoyl chloride under
the similar reaction conditions to that of Beletskaya’s report; however,
the yield of Se-phenyl selenobenzoate (7) was low (24%).
(18) Tanaka disclosed that the reaction of PhSeSnMe3 with Pt(PEt)3
took place rapidly (<10 min) at room temperature to afford trans-Pt-
(SePh)(SnMe3)(PEt3) in 85% isolated yield. See; Han, L.-B.; Shinoda,
S.; Tanaka, M. J . Am. Chem. Soc. 1997, 119, 8135.
3600 J . Org. Chem., Vol. 68, No. 9, 2003

Phenyl Tributylstannyl Selenide as a Reagent
TABLE 2. Syn th esis of Va r iou s r-P h en ylselen o
SCHEME 1. P la u sible Rea ction P a th
Ca r bon yl Com p ou n d sa
(2) Syn th esis of r-P h en ylselen o Ca r bon yl Com -
p ou n d s. R-Phenylseleno carbonyl compounds were use-
ful intermediates for the generation of the enolate anion20
and R-carbonyl carbon radicals21 in organic synthesis, and
much effort is being devoted to accomplish the synthesis
of R-phenylseleno carbonyl compounds.22 Thus, we have
examined the palladium-catalyzed reaction of PhSeSnBu3
(1) with R-bromocarbonyl compounds (6). When 1 was
allowed to react with R-bromoacetophenone (6a ) in the
presence of Pd(PPh3)4 (5 mol %) at 80 °C for 6 h,
R-phenylseleno acetophenone (7a ) was obtained in 90%
yield (entry 1, Table 2). Similarly, the palladium com-
plex catalyzed the coupling of p-methyl-, p-cyano-, p-
chloro-, and p-nitro-R-bromoacetophenone to give the cor-
responding R-phenylselenoacetophenones in moderate
yields (entries 2 and 4-6). For p-methoxy-R-bromoace-
tophenone, the yield of coupling product was low under
reaction conditions similar to those for R-bromoacetophe-
none; however, the yield of product was improved by
elevating the reaction temperature (110 °C) (entry 3). In
the case of R-chloroacetophenone, the yield of R-phenylse-
lenoacetophenone was low (22%) (entry 7). In this coup-
ling reaction, the yields of products were influenced by
the steric effect of the R-position. Although the coupling
reaction of 1 with R-bromopropiophenone gave R-phe-
a
Reaction conditions: 1 (0.25 mmol), R-bromo carbonyl com-
(19) Rossi has reported the synthesis of (E)-1-alkenyl phenylsulfides
by the palladium-catalyzed reaction of 1-alkenyl bromides with tri-
alkylstannyl phenylsulfide. In this paper, they proposed that the first
step of this reaction was the generation of vinylpalladium bromide
species by the reaction of 1-alkenyl bromides with low-valent palladium
species. See: Carpita, A.; Rossi, R.; Scamuzzi, B. Tetrahedron Lett.
1989, 30, 2699.
(20) See for examples: (a) Falcone, S. I.; Munk, M. E. Synth.
Commun. 1979, 9, 719. (b) Zima, G.; Barnum, C.; Liotta, D. J . Org.
Chem. 1980, 45, 2736. (c) Reich, H. J .; Shah, S. K.; Gold, P. M.; Olson,
R. E. J . Am. Chem. Soc. 1981, 103, 3112. (d) Liotta, D.; Saindane, M.;
Barnum, C. J . Am. Chem. Soc. 1981, 103, 3224. (e) Liotta, D.; Saindane,
M.; Brothers, D. J . Org. Chem. 1982, 47, 1598. (f) Piettre, S.; J anousek,
Z.; Viehe, H. G. Synthesis 1982, 1083. (g) Denis, J . N.; Krief, A. J .
Chem. Soc., Chem. Commun. 1983, 229. (h) Reich, H. J .; Kelly, M. J .;
Olson, R. E.; Holtan, R. C. Tetrahedron 1983, 39, 949. (i) Tsuda, Y.;
Hosoi, S.; Nakai, A.; Ohshima, T.; Sakai, Y.; Kiuchi, F. J . Chem. Soc.,
Chem. Commun. 1984, 1216. (j) Eaton, P. E.; Bunnelle, W. H.
Tetrahedron Lett. 1984, 25, 23. (k) Lerouge, P.; Paulmier, C. Tetrahe-
dron Lett. 1984, 25, 1987.
(21) See for examples: (a) Toru, T.; Watanabe, Y.; Yoneda, Y.; Ueno,
Y. Tetrahedron Lett. 1990, 31, 6669. (b) Toru, T.; Watanabe, Y.; Yoneda,
T.; Okumura, T.; Ueno, Y. Bull. Chem. Soc. J pn. 1993, 66, 3030
including references therein.
(22) (a) Back, T.; Kerr, R. Tetrahedron Lett. 1982, 23, 3241. (b)
Sonoda, N.; Miyoshi, N.; Yamamoto, T.; Kambe, N.; Murai, S. Tetra-
hedron Lett. 1982, 23, 4813. (c) Magnus, P.; Rigollier, P. Tetrahedron
Lett. 1992, 33, 6111. (d) Cossy, J .; Furet, N. Tetrahedron Lett. 1993,
34, 7755. (e) Paulmier, C.; Houllemare, D.; Ponthieux, S.; Outurquin,
F. Synthesis 1997, 101 and references cited therein.
pound (0.25 mmol), Pd(PPh3)4 (5 mol %) and toluene (2 mL) at 80
°C for 6 h. GC yield. c At 110 °C.
b
nylselenopropiophenone in 84% yield, in the case of
R-bromo-R-methylpropiophenone, the yield of R-phenylse-
leno ketone was low compared with R-bromopropiophe-
none (entries 8 and 9). An R-bromo dialkyl ketone such
as 2-bromo-3-pentanone as well as R-bromoalkyl phenyl
ketone was coupled with 1 giving 2-phenylseleno-3-
pentanone in 48% yield (entry 10). Similarly, R-pheylse-
leno esters were successfully synthesized by the palladium-
catalyzed reaction of 1 with R-bromo esters (entries 11
and 12).
In summary, the coupling reaction of PhSeSnBu3,
which is stable against air and moisture, with acyl or
aroyl chlorides in the presence of a catalytic amount of
Pd(PPh3)4 efficiently proceeded to give the corresponding
selenol esters in moderate to good yields. The palladium
complex also acts as a catalyst for the coupling of
PhSeSnBu3 with R-halo carbonyl compounds to give the
corresponding R-phenylseleno carbonyl compounds in
moderate yields. This method has some noteworthy
J . Org. Chem, Vol. 68, No. 9, 2003 3601

Nishiyama et al.
reduced pressure. The residual oil was purified by distillation
with Kugelrohr under reduced pressure (1 mmHg) to yield
PhSeSnBu3 (1) (72%): 1H NMR (CDCl3/TMS) δ 0.87 (t, J )
7.6 Hz, 9H), 1.11 (t, J ) 7.6 Hz, 6H), 1.28 (sextet, J ) 7.6 Hz,
6H), 1.50 (quintet, J ) 7.6 Hz, 6H), 7.12-7.19 (m, 3H), 7.52-
7.55 (m, 2H); 13C NMR (CDCl3/TMS) δ 13.79, 14.24, 27.17,
29.00, 126.40, 128.77, 136.81, 136.85
features: (i) the use of stable organoselenium reagent
against air and moisture; (ii) the high and moderate yield
preparation method of organoselenium compounds; (iii)
neutral reaction conditions; and (iv) ease of operation. A
wide range of organoselenium compounds were synthe-
sized successfully by employing this palladium-catalyzed
reaction system.
Gen er a l P r oced u r e for th e P d (P P h 3)4-Ca ta lyzed Syn -
th esis of Se-P h en yl Selen ol Ester s by th e Rea ction of
P h SeSn Bu 3 w ith Ar oyl or Acyl Ch lor id es. Aroyl or acyl
chlorides (0.25 mmol) and PhSeSnBu3 (112 mg, 0.25 mmol)
were added to a toluene (2 mL) solution of Pd(PPh3)4 (3 mg,
0.0025 mmol), and the reaction mixture was stirred at 25 °C
for 6 h under nitrogen atmosphere. After the reaction was
complete, H2O was added to the resulting solution and
extracted with diisopropyl ether (×5). The combined organic
layer was washed with brine and aq KF and dried over MgSO4.
The organic solvent was removed under reduced pressure.
Exp er im en ta l Section
Gen er a l P r oced u r e. 1H and 13C NMR spectra were re-
corded on 400 and 99.5 MHz spectrometers using CDCl3 as
solvent with tetramethylsilane as the internal standard. IR
spectra were obtained on an FT-IR spectrophotometer. Mass
spectra were measured on GC-MS. Gass chromatography
(GC) was carried out on a spectrometer flame-ionizing detector
using a capillary column. R-Bromo carbonyl compounds, pal-
ladium complexes, and tributylstannyl chloride were com-
mercially available and used without purification. Aroyl and
acyl chlorides and solvents were commercially available and
purified by the usual methods before use. Diphenyl diselenide
Purification by column chromatography (C6H14/AcOEt
50/1) on silica gel gave the corresponding Se-phenyl selenol
esters.
)
Gen er a l P r oced u r e for th e P d (P P h 3)4-Ca ta lyzed Rea c-
tion of P h SeSn Bu 3 w ith R-Br om o Ca r bon yl Com p ou n d .
R-Bromo carbonyl compounds (0.25 mmol) and PhSeSnBu3
(112 mg, 0.25 mmol) were added to a toluene (2 mL) solution
of Pd(PPh3)4 (15 mg, 0.0125 mmol), and the reaction mixture
was stirred at 80 °C for 6 h under nitrogen atmosphere. After
the reaction was complete, H2O was added to the resulting
solution and extracted with diisopropyl ether (×5). The
combined organic layer was washed with brine and aq KF and
dried over MgSO4. The organic solvent was removed under
reduced pressure. Purification by column chromatography
(C6H14/AcOEt ) 6/1) on silica gel gave the corresponding
R-phenylseleno carbonyl compounds.
26
was synthesized by the literature procedure.
P r ep a r a t ion of P h en yl Tr ib u t ylst a n n yl Selen id e.
Bu3SnCl (5.208 g, 16 mmol) was added to the PhSeNa (16
mmol), which was generated in situ by the literature method,27
in EtOH/THF (2 mL/30 mL) solution at 0 °C and stirred at 25
°C for 3 h. After the reaction was complete, H2O was added to
the resulting solution and extracted with diisopropyl ether
(×5). The combined organic layer was washed with brine and
dried over MgSO4. The organic solvent was removed under
(23) It has already reported that palladium-catalyzed coupling of
R-halo carbonyl compounds with allyl- and acetonyltin24 or organ-
otins.25
(24) Simpson, J . H.; J . K. Stille, J . Org. Chem. 1985, 50, 1759.
(25) Bhatt, B. K.; Shin, S. D.; Falck, J . R.; Mioskowski, C. Tetra-
hedron Lett. 1992, 33, 4885.
(26) Reich, H. J .; Renga, J . M.; Reich, I. L. J . Am. Chem. Soc. 1975,
97, 5434.
(27) Liotta, D.; Markiewicz, W.; Stantiesteban, H. Tetrahedron Lett.
1977, 50, 4365.
Su p p or t in g In for m a t ion Ava ila b le: Copies of spectra
(1H, 13C and IR) for all coupling products. This material is
available free of charge via the Internet at http://pubs.acs.org.
J O026894I
3602 J . Org. Chem., Vol. 68, No. 9, 2003