Preparation of triarylantimony(V) diacetates and palladium-catalyzed cross-coupling and carbonylative cross-coupling of triarylantimony(V) diacetates and dichlorides with organostannanes

Article abstract of DOI:10.1016/S0022-328X(00)00386-7

Triarylstibines react with iodobenzene diacetate in dichloromethane to afford triarylantimony(V) diacetates. The cross-coupling and carbonylative cross-coupling of triarylantimony(V) diacetates and dichlorides with organostannanes was accomplished in the presence of PdCl₂ (5 mol%) in CH₃CN at room temperature.

Full text of DOI:10.1016/S0022-328X(00)00386-7

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 610 (2000) 38–41
Preparation of triarylantimony(V) diacetates and
palladium-catalyzed cross-coupling and carbonylative
cross-coupling of triarylantimony(V) diacetates and dichlorides
with organostannanes
Suk-Ku Kang *, Hyung-Chul Ryu, Sang-Woo Lee
Department of Chemistry and Institute for Basic Sciences, Natural Science Campus, Sungkyunkwan Uni6ersity, Suwon 440-746, South Korea
Received 5 April 2000; received in revised form 6 June 2000
Abstract
Triarylstibines react with iodobenzene diacetate in dichloromethane to afford triarylantimony(V) diacetates. The cross-coupling
and carbonylative cross-coupling of triarylantimony(V) diacetates and dichlorides with organostannanes was accomplished in the
presence of PdCl (5 mol%) in CH CN at room temperature. © 2000 Published by Elsevier Science S.A. All rights reserved.
2
3
Keywords: Organoantimony compounds; Palladium-catalyzed; Cross-coupling; Carbonylative; Organostannanes
2
PdCl (5 mol%)
Ar Sb(OAc) + RSnBu3
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁ
Ar–R
3
2
1. Introduction
CH CN, rt
3
1a−b
R=vinyl, aryl
(1)
Organoantimony compounds have been recently ap-
PdCl
2
(5 mol%)
Ar Sb(OAc) +RSnBu +CO (1 atm) ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁ
3
2
3
plied for synthetic organic reactions [1]. Most of these
works are focused on trivalent triarylstibines or tri-
butylstibines [2] as well as pentavalent stibonium com-
pounds such as tetraphenylstibonium iodide and
methoxide [3]. Recently, palladium-catalyzed carbony-
lation [4] of triarylstibines and acylation of triarylstibi-
nes have been reported. Coupling reactions of
pentaarylantimony with carbon nucleophiles or elec-
trophiles are known [5]. Although different from the
other 15 group elements such as phosphorous, arsenic,
and bismuth, the reaction of triarylantimony com-
pounds bearing five covalent bonds exhibited unique
reactivity in carbon–carbon bond formation [6]. There-
fore we wish to describe a novel method of preparation
of triarylantimony diacetates, and the palladium-cata-
lyzed cross-coupling and carbonylative cross-coupling
of triarylantimony diacetates and triphenylantimony
dichloride (Eqs. (1)–(4)).
CH CN, rt
3
1a−b
ArCOR
Ph SbCl +RSnBu
3
(2)
(3)
2
PdCl (5 mol%)
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁ
Ar–R
3
2
1c
3
CH CN, rt
PdCl
2
(5 mol%)
Ph SbCl +RSnBu +CO (1 atm) ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁ
3
2
3
3
CH CN, rt
ArCOR
(4)
Triarylantimony(V) diacetates are usually prepared
by the oxidation of triarylantimony with t-butyl hy-
droperoxide [7], t-butyl peracetate [8], and Hg(II) or
Cu(II) salts [9]. Herein we wish to report the prepara-
tion of triarylantimony(V) diacetates utilizing
PhI(OAc)2 as an oxidizing agent. This procedure is
more simple and convenient than the method reported.
Thus triarylantimony(V) diacetates 1a and 1c were
prepared by reaction of triarylantimony(III) with
PhI(OAc) by stirring in CH Cl at room temperature
2
2
2
for 6–7 h (Eq. (5)) [10].
CH Cl
2 2
, rt, 7 h
Ar Sb+PhI(OAc) ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁ Ar Sb(OAc)
3
2
3
2
1
a [11] Ar=Ph
73%
*
Corresponding author. Tel.: +82-31-2907064; fax: +82-31-
1b [12] Ar=p-Tolyl 77%
2
907064.
E-mail address: skkang@chem.skku.ac.kr (S.-K. Kang).
(5)
0
022-328X/00/$ - see front matter © 2000 Published by Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00386-7

S.-K. Kang et al. / Journal of Organometallic Chemistry 610 (2000) 38–41
39
2
. Results and discussion
yields (entries 4–5). When triphenylantimony(V) diac-
etate (1a) was treated with a-substituted stannane 2e,
(E)-cinnamic ester (3e) was obtained as the sole product
via the mechanism of cine substitution [16] (entry 5).
This coupling method was extended to carbonylative
cross-coupling to prepare aryl ketones [17]. The palla-
dium-catalyzed carbonylative cross-coupling under at-
mospheric pressure of carbon monoxide was achieved
at room temperature under mild conditions. The reac-
tion of 1a with phenyltributylstannane (2f) under atmo-
spheric pressure of carbon monoxide in the presence of
PdCl (5 mol%) in CH CN at room temperature for 3 h
The results of the palladium-catalyzed cross-coupling
and carbonylative cross-coupling of triarylantimony(V)
diacetates with organostannanes (Scheme 1) are sum-
marized in Table 1. Triarylantimony(V) diacetates (1a)
[
11] reacted with p-methoxyphenyltributylstannane (2a)
in the presence of PdCl (5 mol%) in CH CN at room
2
3
temperature for 7 h to afford the coupled product 3a in
8% yield (entry 1). Among all the catalysts tested
PdCl , Pd(OAc) , Pd (dba) ·CHCl , Pd(PPh ) ], PdCl
7
[
2
2
2
3
3
3 4
2
(5 mol%) and Pd(OAc) (5 mol%) proved to be the
2
2
3
most efficent and PdCl (5 mol%) was the preferred
afforded benzophenone (4a) in 85% yield (entry 6).
Under the same conditions, 2-thienyl- and 2-furylstan-
nanes 2b and 2c were readily coupled to give the
ketones 4b [18] and 4c [19], respectively (entries 7–8).
This carbonylative cross-coupling method was also ap-
plied to alkenyl- and alkynyl-substituted stannanes.
Thus when 2g and 2h were treated with 1a under
atmospheric pressure of carbon monoxide, the alkenyl-
and alkynyl-substituted ketones 4d [20] and 4e [21] were
2
catalyst. As a solvent, CH CN was the most suitable
3
among the solvents DMF, NMP, MeOH, DME tested.
Under the same conditions, the coupling of 1a with
2-furyl- and 2-thienylstannanes 2b and 2c [12] provided
the cross-coupled products 3b [13] and 3c [14] in 90%
yields, respectively (entries 2–3). This coupling method
was also applied to alkenyl stannanes 2d and 2e to give
the substituted alkenes 3d and 3e [15] in 80 and 54%
Scheme 1.
Table 1
The palladium-catalyzed cross-coupling and carbonylative cross-coupling of triarylantimony diacetates with organostannanes
Entry
Organoantimony compounds
Organostannanes
Products
Isolated yields (%)
1
2
3
4
5
6
7
8
9
0
1
2
3
la
la
la
la
la
la
la
la
la
la
lb
lb
lb
2a
2b
2c
2d
2e
2f
2b
2c
2g
2h
2b
2c
2h
3a
3b
3c
3d
3e
4a
4b
4c
4d
4e
4f
78
90
90
80
54
85
81
81
83
77
81
71
75
1
1
1
1
4g
4h

4
0
S.-K. Kang et al. / Journal of Organometallic Chemistry 610 (2000) 38–41
Scheme 2.
respectively formed in 83 and 77% yields (entries 9–10).
For the tri(p-tolyl)antimony(V) diacetate (1b) [9] the
carbonylative coupling with 2b and 2c gave the coupled
ketones 4f [22] and 4g (entries 11–12). Finally, 1b
coupled in the presence of carbon monoxide with
alkynyl-substituted stannane 2h to afford the ketone 4h
in 75% yield (entry 13).
Alternatively, the palladium-catalyzed cross-coupling
and carbonylative cross-coupling of the readily available
triphenylantimony(V) dichloride (1c) with organostan-
nanes (Scheme 2) are summarized in Table 2. 1c was
readily coupled with stannanes 2a, 2b, and 2c to afford
the coupled products 3a–3c in 81–90% yields (entries
All solvents were used after distillation. Palladium chlo-
ride was purchased from Aldrich Chem. Inc. NMR
spectra were recorded on a Varian (500 MHz)
spectrometer.
3.2. General procedure for the oxidation of
triarylantimony to triarylantimony diacetate
A mixture of triarylantimony (2.00 mmol) and
iodobenzene diacetate (2.20 mmol) in dichloromethane
(20 ml) was stirred at room temperature for 7 h. The
solvent was concentrated under reduced pressure to a
small volume. A mixture of diethyl ether–pentane was
added and the solution kept overnight at −15°C. The
solid was filtered and recrystallized from a mixture of
dichloromethane and pentane.
1
–3). When the a-substituted alkenylstannane 2e was
treated with 1c, the coupled product 3g with cine
substitution was obtained as the sole product (entry 4).
This method was also extended to carbonylative cross-
coupling. The reaction of triphenylantimony(V) dichlo-
ride (1c) with stannanes 2f, 2b, and 2c provided the
coupled ketones 4a, 4b, and 4c in 88–90% yields (entries
Table 2
The palladium-catalyzed cross-coupling and carbonylative cross-cou-
pling of triphenyl antimony dichloride (1c) with organostannanes
5
–7). Finally, 1c was utilized in carbonylative coupling
with alkenyl- and alkynyl-substituted stannanes 2g and
h to afford enone 4d and ynone 4e in 81 and 80%
2
Entry
Organostannanes
Products
Isolated yields (%)
yields, respectively (entries 8–9).
Although the detailed mechanism remains to be
clarified, it is presumed that oxidative addition of anti-
mony compounds forms the intermediate A, which is
subjected to transmetallation and coupling to give the
coupled product (Scheme 3).
In conclusion triarylantimony(V) diacetates were pre-
pared conveniently and cross-coupling and carbonyla-
tive cross-coupling of triarylantimony(V) derivatives
with organostannanes were achieved in the presence of
PdCl2 (5 mol%) at room temperature under mild
conditions.
1
2
3
4
5
6
7
8
9
2a
2b
2c
2e
2f
2b
2e
2g
2h
3a
3b
R
3e
4a
4b
4c
4d
4e
81
88
90
56
90
88
88
81
80
3. Experimental
3.1. Materials
Ph SbCl is commercially available from Aldrich
3
2
Chem. Inc. and was used without further purifications.
Scheme 3.

S.-K. Kang et al. / Journal of Organometallic Chemistry 610 (2000) 38–41
41
Triphenylantimony(V) diacetate (1a): m.p. 210–
BK-21 graduate fellows sponsored by the Ministry of
Education.
1
2
12°C ([23] 208–209°C), H-NMR (CDCl ): l 1.83 (s,
3
6
H), 7.48 (m, 9H), 7.99 (m, 6H). Tri(p-tolyl)antimony-
1
(
V) diacetate (1b): m.p. 157–159°C, H-NMR (CDCl ):
3
l 1.82 (s, 6H), 2.39 (s, 9H), 7.27 (d, 6H, J=8), 7.86 (d,
References
6H, J=8 Hz).
[
1] (a) L.D. Freeman, G.O. Doak, in: F.R. Hartly (Ed.), The
Chemistry of the Metal–Carbon Bond, vol. 5, Wiley, New York,
3
.3. Typical procedure for the cross-coupling of
organostannanes with organoantimony(V) compounds
1
989, pp. 397. (b) M. Fujiwara, K. Hitomi, A. Baba, H. Mat-
suda, Chem. Lett. (1994) 875. (c) M. Fujiwara, M. Tanaka, A.
Baba, H. Ando, Y. Souma, Tetrahedron Lett. (1995) 4849.
2] Y.-Z. Huang, Acc. Chem. Res. 25 (1992) 182.
3] (a) M. Fujiwara, M. Imada, A. Baba, H. Matsuda, J. Org.
Chem. 53 (1988) 5974. (b) M. Fujiwara, A. Baba, H. Matsuda,
Bull. Chem. Soc. Jpn. 63 (1990) 1069. (c) M. Fujiwara, A.
Hitomi, H. Matsuda, Synthesis (1990) 106.
To a mixture of triphenylantimony diacetate (1a)
412 mg, 1.00 mmol) and PdCl (8.9 mg, 5 mol%) was
2
added 2-(tributylstannyl)thiophene (2c) (373 mg, 1.00
mmol) under N2 charged at room temperature in
[
[
(
CH CN (20 ml). The reaction mixture was stirred at
3
[
[
4] (a) C.S. Cho, K. Tanabe, O. Itoh, S. Uemura, J. Org. Chem. 60
room temperature for 3 h, extracted with ether (3×20
ml), washed with water (3×20 ml). The organic layer
(
1995) 274. (b) C.S. Cho, S.I. Motofusa, S. Uemura, Tetrahe-
dron. Lett. 35 (1994) 1739. (c) C.S. Cho, S.I. Motofusa, K. Ohe,
S. Uemura, Bull. Chem. Soc. Jpn. 69 (1996) 2341. (d) Rh(I)-cat-
alyzed carbonylation of triarylbismuthines. See: C.S. Cho, Y.
Yoshimori, S. Uemura, Bull. Chem. Soc. Jpn. 68 (1995) 950.
5] (a) M. Fujiwara, M. Tanaka, A. Baba, H. Ando, Y.J. Souma,
Organomet. Chem. 525 (1996) 39. (b) M. Fujiwara, M. Tanaka,
A. Baba, H. Ando, Y. Souma, J. Organomet. Chem. 508 (1996)
was dried over anhydrous MgSO and evaporated in
4
vacuo. The crude product was separated by SiO2
column chromatography (Hexanes, R =0.52) to afford
f
coupled product 2-phenylthiophene (3c) (144 mg, 90%),
1
H-NMR (400 MHz, CDCl ) l 7.09 (dd, 1H, J=5.1,
3
3
2
7
1
.5), 7.27 (m, 2H), 7.32 (dd, 1H, J=3.5 Hz), 7.38 (m,
4
9.
H), 7.62 (m, 2H). IR (KBr)=3070, 1608, 1477, 832,
[
[
6] (a) Y.-Z. Hwang, Y. Liao, J. Org. Chem. 56 (1991) 1381. (b)
L.-T. Zhang, Y.-Z. Huang, H.-X. Jiang, J. Duan-Mu, Y. Liao, J.
Org. Chem. 57 (1992) 774.
7] A.V. Guschin, V.A. Dodonov, R.-I. Usyatinsky, E.R. Kore-
shkova, B.B. Tipanov, Izv. Akad. Nauk. Ser. Khim. (1994) 1302.
Chem. Abstr. 122 (1995) 265525u.
8] A.V. Guschin, E.E. Dyomina, V.A. Dodonov, Izv. Akad. Nauk.
Ser. Khim. (1995) 964. Chem. Abstr. 124 (1996) 29925.
9] S.N. Bhattacharya, M. Singh, Indian J. Chem. Sect. A 18 (1979)
−
1
08 cm . MS (EI): m/e (relative intensity)=160 (100),
28 (13), 115 (34), 102 (5), 89 (7).
3
.4. Typical procedure for the carbonylati6e
cross-coupling of organostannanes with
organoantimony(V) compounds
[
[
5
15. Chem. Abstr. 92 (1980) 215505e.
To a mixture of triphenylantimony diacetate (1a)
[
10] Triarylantimony(V) compounds (1a–b) were prepared following
the procedure reported for the preparation of their bismuth
analogues: S. Combes, J.-P. Finet, Tetrahedron 54 (1998) 4313.
(
412 mg, 1.00 mmol) and PdCl (8.9 mg, 5 mol%) was
2
added 2-(tributylstannyl)furan (2b) (358 mg, 1.00
mmol) under atmospheric pressure of CO at room
[11] J. Havranek, J.M. Mleziva, A. Lycka, J. Organomet. Chem. 157
1978) 163.
12] S.N. Bahahacharya, M. Singh, Indian J. Chem. Sect. A 18 (1979)
15. Chem. Abs. 92 (1980) 215506e.
13] A. Pelter, M. Rowlands, G. Clements, Synthesis (1987) 51.
(
temperature in CH CN (20 ml). The reaction mixture
3
[
[
was stirred at room temperature for 6 h, extracted with
ether (3×20 ml), washed with water (3×20 ml). The
5
organic layer was dried over anhydrous MgSO and
4
[14] E. Negishi, F.R.T. Luo, H. Matsushita, Heterocycles 18 (1982)
117.
evaporated in vacuo. The crude product was separated
[
15] S.K. Kang, T. Yamaguchi, P.S. Ho, W.Y. Kim, S.K. Yoon,
Tetrahedron Lett. 58 (1997) 1947.
by SiO column chromatography (EtOAc–hexanes 1:
2
1
0, R =0.46) to afford coupled product 2-benzoylfuran
f
[
16] (a) K. Kikukawa, H. Uemura, T. Matsuda, J. Organomet.
Chem. 311 (1986) C44. (b) G. Stork, R.C.A. Isaacs, J. Am.
Chem. Soc. 112 (1990) 7399. (c) C.A. Busacca, J. Swestock, R.E.
Johnson, T.R. Bailey, L. Musza, C.A. Rodger, J. Org. Chem. 59
1
(
4b) (139 mg, 81%), H-NMR (400 MHz, CDCl ) l
3
6
7
1
.58 (m, 1H), 7.23 (m, 1H), 7.48 (m, 2H), 7.58 (m, 1H),
.70 (m, 1H), 7.90 (m, 2H). IR (KBr)=3134, 2342,
−
1
(
1994) 7553. (d) V. Farina, M.A. Hossian, Tetrahedron Lett. 37
647, 1563, 1464 cm . MS (EI): m/e (relative inten-
+
(1996) 6997. (e) S.-H. Chen, Tetrahedron Lett. 38 (1997) 4741.
17] Review: J.J. Brunet, R. Chauvin, Chem. Soc. Rev. (1995) 89.
18] R. Benassi, U. Folli, D. Iarossi, I. Schenetti, F. Taddei, J. Chem.
Soc. Perkin Trans. I (1987) 1443.
sity)=172 (M , 100), 105 (94), 95 (58), 77 (97).
[
[
Acknowledgements
[19] S.K. Kang, K.H. Lim, P.S. Ho, S.K. Yoon, H. Son, J. Synth.
Commun. 28 (1998) 1481.
[
[
[
[
20] S. Thomas, N. Stephan, J. Organomet. Chem. 430 (1992) C5.
21] L. Delaude, A.M. Masdeu, H. Alper, Synthesis (1994) 1149.
22] G. Zadel, E. Breitmaier, Angew. Chem. 104 (1992) 1070.
23] J. Bordner, G.O. Doak, T.S. Everett, J. Am. Chem. Soc. 108
(1986) 4206.
The authors wish to acknowledge the financial sup-
port of the Korea Research Foundation in the Program
Year 1997 and KOSEF-CMDS (Center for Molecular
Design and Synthesis). H.-C. Ryu and S.-W. Lee are
.