Palladium-catalyzed coupling of tetraphenylbismuth(V) derivatives with methyl acrylate

Article abstract of DOI:10.1134/S1070363206080147

Tetraphenylbismuth(V) derivatives of the general formula Ph₄BiX [X = OSO₂C₆H₄Me-4, OC₆H ₂(NO₂)₃-2,4,6, OC₆H ₂(NO₂-4)(Br₂-2,6), OSO₂C ₆H₃(OH)(COOH)] react with methyl acrylate in the presence of palladium dichloride (1:3:0.04 molar ratio) in acetonitrile at 20°C to form the cross-coupling products, methyl cinnamate (0.17-0.54 mol mol ^-1 starting bismuth compound) and methylhydrocinnamate (0.10-0.73 mol mol^-1), diphenyl (0.06-0.80 mol mol^-1), and benzene (0.02-0.36 mol mol^-1). The highest C-phenylating activity is shown by Ph₄BiOSO₂C₆H₄Me-4. The mechanisms with the palladium-catalyzed cross-coupling reactions are suggested. Nauka/Interperiodica 2006.

Full text of DOI:10.1134/S1070363206080147

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 8, pp. 1253 1255.
Pleiades Publishing, Inc., 2006.
Original Russian Text A.V. Gushchin, Yu.B. Malysheva, D.Yu. Kosov, V.V. Sharutin, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 8,
pp. 1305 1308.
Palladium-Catalyzed Coupling of Tetraphenylbismuth(V)
Derivatives with Methyl Acrylate
a
a
a
b
A. V. Gushchin , Yu. B. Malysheva , D. Yu. Kosov , and V. V. Sharutin
a
Lobachevsky Nizhni Novgorod State University, pr. Gagarina 23, Nizhni Novgorod, 603950 Russia
e-mail: gushchin@mail.nnov.ru
b
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received September 2, 2005
Abstract Tetraphenylbismuth(V) derivatives of the general formula Ph BiX [X = OSO C H Me-4,
4
2 6 4
OC H (NO ) -2,4,6, OC H (NO -4)(Br -2,6), OSO C H (OH)(COOH)] react with methyl acrylate in the
6
2
2 3
6
2
2
2
2 6 3
presence of palladium dichloride (1:3: 0.04 molar ratio) in acetonitrile at 20 C to form the cross-coupling
1
products, methyl cinnamate (0.17 0.54 mol mol starting bismuth compound) and methylhydrocinnamate
1
1
1
(
0.10 0.73 mol mol ), diphenyl (0.06 0.80 mol mol ), and benzene (0.02 0.36 mol mol ). The highest
C-phenylating activity is shown by Ph BiOSO C H Me-4. The mechanisms with the palladium-catalyzed
4
2 6 4
cross-coupling reactions are suggested.
DOI: 10.1134/S1070363206080147
Organobismuth compounds always attract the re-
searchers’ attention in connection with the develop-
ment of the organic synthesis. They are highly reac-
tive because of the low Bi C bond energy; under mild
conditions, they can enter the coupling reactions with
organic substrates to form new C O, C N, and C C
bonds. The catalytic coupling reactions of bismuth
compounds with unsaturated organic substrates are
being actively studied. C-Phenylation of unsaturated
compounds with triphenylbismuth in the presence of
In this study we examined the coupling reaction of
unsaturated substrate I with tetraphenylbismuth com-
pounds Ph BiX and compared the product yields and
4
selectivity with the known data for alkenyl (R BiX)
4
and phenyl (Ph BiX ) bismuth derivatives.
3
2
Tetraphenylbismuth halides and carboxylates
cannot be used as starting organobismuth compounds
because they are unstable at room temperature. There-
fore, we chose more stable tetraphenylbismuth phe-
nolates and sulfonates. The reactions were carried out
under typical conditions previously chosen for study-
ing triphenylbismuth carboxylates (Ph :I:PdCl ratio
stoichiometric amounts of Pd(OAc) was reported for
2
the first time in [1]. Later a similar system was
studied as applied to other substrates [2, 3]. C-phenyla-
4
2
1
:3:0.04, acetonitrile, 20 C, 24 h).
tion with a trivalent bismuth derivative (Ph BiCl) in
2
the presence of catalytic amounts of palladium was
described in [4].
Ph BiX + CH =CHCO Me
4
2
2
2
I
Triphenylbismuth carboxylates, halides, phenolates,
and sulfonates were studied as reagents for mild
C-phenylation of methyl acrylate I at 20 50 C. Two
cross-coupling products, methyl cinnamate II and
methyl hydrocinnamate III, and also diphenyl IV and
benzene V were detected. The yields and ratio of the
products significantly depend on the structure of acid
residue [5 7]. With an alkenyltriphenylbismuthonium
salt taken as a C-phenylating agent for ethyl acrylate,
a series of products were obtained, including the
product of coupling of alkenyl and phenyl groups of
the starting organobismuth compound, the products
of coupling of both groups with ethyl acrylate, and
also diphenyl and benzene [8].
0.04 mol PdCl , 20 C, 24 h
2
PhCH=CHCO Me
2
CH CN
3
II
+ PhCH CH CO Me + Ph + PhH,
2
2
2
2
III
OSO C H Me-4, OC H (NO ) -2,4,6, OC H
6 2
IV
V
X
=
2
6
4
6
2
2 3
(
NO -4)Br -2,6, OSO C H (OH)(COOH).
2 2 2 6 3
C-Phenylation of ester I with tetraphenylbismuth
tosylate leads to the formation of the coupling prod-
ucts in high1 yields. The yield of II was
0.54 mol mol starting organobismuth compound;
1
that of III, 0.73 mol mol ; and that of IV,
0.68 mol mol 1 (see table, run no. 1). Benzene was
1253

1254
GUSHCHIN et al.
Influence of the structure of organobismuth compounds on the yield of the products of methyl acrylate phenylation with
a
the Ph BiX + PdCl (3: 1: 0.04) system
4
2
Yield, mol mol 1 Ph BiX
4
Exp. no.
Organobismuth compound
II
III
IV
V
Phb
1
2
3
4
5
Ph BiOSO C H Me-4
0.54
0.30
0.22
0.17
0.89
0.73
0.63
0.15
0.10
0.21
0.68
0.49
0.80
0.06
0.29
0.02
0.14
0.36
0.08
0.12
2.65
2.05
2.33
0.47
1.80
4
2 6 4
Ph BiOC H (NO ) -2,4,6
4
6
2
2 3
c
Ph BiOC H (NO -4)(Br -2,6)
4 6 2 2 2
Ph BiOSO C H (OH)(COOH)
4 2 6 3
+
2
[(Ph Bi) OSO C H Me -2,5] [Ph Bi I ]
4
2
2
6
3
2
2
2
2 6
a
b
c
Reactions were carried out in CH CN at 20 C for 24 h in air. ( Ph) Total consumption of phenyl groups. Organobismuth
3
compound:methyl acrylate ratio 1:30.
1
obtained in a low yield (0.02 mol mol ). The use of
tetraphenylbismuth phenolates instead of tosylate
decreases the yields of the cross-coupling products II
PdCl2
Ph BiX + CH =CHCO Me
PhCH=CHCO Me
4
2
2
2
+
Ph Bi + HX.
(4)
3
1
and III to 0.22 0.30 and 0.15 0.63 mol mol , re-
As mentioned previously, the phenylation of
methyl acrylate I with the formation of II was always
accompanied by hydrogenation phenylation of I yield-
ing methyl hydrocinnamate III. Its yield in all the
experiments with tetraphenylbismuth tosylate and
picrate was 1.5 2 times higher than the yield of me-
thyl cinnamate (see table, run nos. 1, 2). The highest
yield of III was 0.73 mol mol 1 with tetraphenylbis-
muth tosylate (see table, run no. 1). In the previously
described reactions with methyl acrylate, methyl
hydrocinnamate was never isolated as the prevalent
product. For example, in the reactions with Ph BiX ,
spectively, and the yield of V increases to 0.14
.36 mol mol 1 (see table, run nos. 2, 3). Thus, tetra-
0
phenylbismuth tosylate and phenolate readily react
with ester I; the consumption of phenyl groups is
1
2
.05 2.65 mol mol (see table, run nos. 1 3). On the
contrary, tetraphenylbismuth salicylsulfonate showed
very low activity (consumption of phenyl groups was
1
0
.47 mol mol ) in formation of all the phenylation
products. In this case, the yield of methyl cinnamate
1
II was 0.17 mol mol ; that of methyl hydrocinnamate
1
III, 0.10 mol mol ; that of diphenyl IV,
1
1
0
.06 mol mol ; and that of benzene, 0.08 mol mol
3
2
its highest yield was 17% with X = OTs [7], and in
(
see table, run no. 4). In the reaction with [(Ph Bi)
4
2
+
2
the reactions with Ph SbX it was 31% with X = Cl
OSO C H Me -2,5] [Ph Bi I ] , the yield of methyl
cinnamate II was 0.89 mol mol ; that of methyl
hydrocinnamate III, 0.21 mol mol ; that of diphenyl
IV, 0.29 mol mol ; and that of benzene V,
4
2
6
3
3
2
2
2 6
1
[9, 11].
1
The suggested scheme of the hydrogenation pheny-
1
lation of methyl acrylate with Ph BiX is based on the
4
0
.12 mol mol 1 (see table, run no. 5).
previously studied reaction with Ph SbCl [10]. The
4
phehylpalladium intermediate formed according to
Eq. (1) enters into the 1,4-cycloaddition reaction with
ester I [Eq. (5)]. The acid released in the course of
phenylation of I to II effects the acidolysis of pal-
We suggested a scheme of this reaction based on
the previously studied reaction of tetraphenylantimony
chloride with methyl acrylate [9, 11]. In the first step,
the organobismuth compound undergoes transmetalla-
ladium alkoxide [Eq. (6)], yielding PdCl and product
tion with PdCl to form the active phenylpalladium
2
2
III.
intermediate PhPdCl [Eq. (1)]. The latter C-phenylates
ester I to give product II [Eq. (2)]. In the course of
this process, Pd(II) is reduced to Pd(0). Further redox
O
OPdCl
PhPdX + CH =CHC
PhCH CH=C
,
2
2
transmetallation with Ph BiX converts the Pd(0)
OMe
OMe
4
(
5)
complex again to PhPdX [Eq. (3)]. The overall
C-phenylation of I is described by Eq. (4).
OPdCl
HCl + PhCH CH=C
PdCl + PhCH CH CO Me.
2 2 2 2
2
OMe
(
6)
Ph BiX + PdCl
Ph BiXCl + PhPdCl, (1)
4
2
3
PhPdCl + CH =CHCO Me
PhCH=CHCO Me
2
2
2
Diphenyl is formed in the processes studied by the
reaction of PhPdX with bismuth derivatives contain-
+
HCl + Pd(0),
(2)
Ph BiX + Pd(0) Ph Bi + PhPdX,
(3)
ing phenyl group via intermediate Ph Pd [Eq. (7)].
4
3
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

PALLADIUM-CATALYZED COUPLING OF TETRAPHENYLBISMUTH(V) DERIVATIVES
1255
PhPdX + Ph [Bi(III, V)]
phase 15% Apiezon L on Chromaton N-AW-DMCS,
Ph + Pd(0) + [Bi(III, V)] X.
(7)
column temperature 230 C. Benzene was determined
on the same column at 80 C.
2
Benzene V is a secondary product in the reactions
under study. It is formed by the reactions of Bi(III)
phenyl derivatives with acids released in the phenyla-
tion reactions [Eq. (2)]:
Reaction of Ph BiOSO C H (OH)(COOH) with
4
2
6
3
methyl acrylate and PdCl (1:3:0.04). A mixture
2
of 0.448
g
of Ph BiOSO C H (OH)(COOH),
4 2 6 3
0
6
.0036 g of PdCl , 0.135 ml of methyl acrylate, and
2
ml of acetonitrile was left for 24 h at room tempera-
HX + Ph Bi
BiX + 3PhH.
(8)
3
3
ture in air. Then the mixture was evaporated at re-
duced pressure, and the residue was passed trough a
column packed with silica gel, elution with 4:1 hex-
ane ethyl acetate. The volatile products in the
condensate and filtrate were determined by GLC.
The benzene yields are low, and this reaction does
not significantly contribute to the catalytic reaction
of organobismuth compounds with methyl acrylate.
Thus, we found that Ph BiX compounds undergo
4
Phenylation with other organobismuth compounds
was performed similarly.
PdCl -catalyzed coupling with methyl acrylate at
2
room temperature. The major reaction products are
diphenyl IV and the cross-coupling products: methyl
cinnamate II and methyl hydrocinnamate III.
REFERENCES
A significant feature of the reactions of tetraphe-
1. Asano, R., Moritani, I., Fujiwara, Y., and Teranishi, S.,
nylbismuth picrate and tosylate (Ph BiX), as com-
Bull. Chem. Soc. Jpn., 1973, vol. 46, no. 9, p. 2910.
4
pared to the recently described reactions of triphenyl-
bismuth picrate and tosylate [7], is a significant in-
crease in the yields of diphenyl IV and methyl hydro-
cinnamate III at a constant yield of methyl cinnamate
2
. Kawamura, T., Kikukawa, K., Takagi, M., and Ma-
tsuda, T., Bull. Chem. Soc. Jpn., 1977, vol. 50, no. 8,
p. 2021.
3
4
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2
Ph BiX is confirmed by a 2.5 3 times higher total
3
2
. Matoba, K., Motofusa, S., Cho, C.S., Ohe, K., and
Uemura, S., J. Organomet. Chem., 1999, vol. 574,
no. 1, p. 3.
consumption of phenyl groups, reaching 2.05
.65 mol mol 1 starting organobismuth compound.
2
We failed to involve all the four phenyl groups in the
reaction under so mild conditions. Contrary to the
above-described tetraphenylbismuth sulfonates and
phenolates, C-phenylation with alkenyltriphenylbis-
muthonium salt gives no hydrophenylation products
5
. Malysheva, Yu.B., Moiseev, D.V., Gushchin, A.V.,
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bismuth derivatives studied exibit higher activity
toward methyl acrylate, which leads to formation of
not only products II and III, but also diphenyl IV and
benzene V. In the case of tetraphenylbismuth picrate
and tosylate, the yield of hydrophenylation product
III exceeds the yield of phenylation product II,
whereas in the case of antimony derivatives methyl
cinnamate II is the major product [9 11].
7
8
9
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on a Tsvet-580 chromatograph equipped with a flame
ionization detector (carrier gas Ar). Methyl hydro-
cinnamate, methyl cinnamate, and diphenyl were
determined on a 2000 3-mm column, stationary
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006