Palladium-catalysed selective aminocarbonylation of 1′,4-diiodostyrene

Article abstract of DOI:10.1016/j.tet.2009.04.012

1′,4-Diiodostyrene possessing both iodo-aryl and iodo-alkenyl functionalities was prepared and used as substrate in palladium-catalysed aminocarbonylation. The corresponding dicarboxamides were obtained as major products in high yields by using several am

Full text of DOI:10.1016/j.tet.2009.04.012

Tetrahedron 65 (2009) 4484–4489
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Palladium-catalysed selective aminocarbonylation of 10,4-diiodostyrene
*
´
´
´
´
Antal Szilagyi, Roland Farkas, Andrea Petz, Laszlo Kollar
Department of Inorganic Chemistry, University of Pe´cs, H-7624 Pe´cs, PO Box 266, Hungary
a r t i c l e i n f o
a b s t r a c t
10,4-Diiodostyrene possessing both iodo-aryl and iodo-alkenyl functionalities was prepared and used as
substrate in palladium-catalysed aminocarbonylation. The corresponding dicarboxamides were obtained
as major products in high yields by using several amine nucleophiles including amino acid methyl esters.
Due to the highly different reactivity of the two iodo-functionalities, the selective aminocarbonylation of
the iodo-vinyl moiety was carried out at atmospheric carbon monoxide pressure resulting in the for-
mation of 4-iodo-phenyl-acrylamides. The latter amides were used as substrates in high pressure amino-
carbonylation resulting in amide–ketocarboxamide type products. The latter functionality was formed
via double carbon monoxide insertion into the iodo–aryl bond.
Article history:
Received 17 December 2008
Received in revised form 20 March 2009
Accepted 2 April 2009
Available online 10 April 2009
Keywords:
Aminocarbonylation
Carbon monoxide
Amino acid
Ó 2009 Elsevier Ltd. All rights reserved.
Palladium
Diiodostyrene
1. Introduction
Iodostyrenes possessing the iodo substituent in the aromatic ring
(2-iodo- and 4-iodostyrene) are known starting materials in polymer
Although palladium-catalysed carbonylations are not as widely
used as direct coupling reactions, such as Heck, Suzuki, Kumada,
Stille and Sonogashira reactions, are among the most favoured
ones due to their simplicity of introducing a carbonyl moiety.1 In
the presence of various nucleophiles such as amines and alcohols,
the synthesis of amides and esters was carried out. Several ap-
plications were aimed at the synthesis of simple building blocks
and at the functionalisation of biologically important skeletons.2
Homogeneous aminocarbonylation plays a special role among
such carbonylations, since the highly active palladium-acyl in-
termediates, formed under catalytic conditions, act as efficient
acylation agents even in the case of amines with low basicity.
Similarly, amines with bulky substituents adjacent to the amine
functionality can be transformed efficiently to carboxamides. In
this way, the conventional methodology based on the carboxylic
acid–carboxylic halide–carboxamide route can be substituted for
a single catalytic reaction.3 Although the enol triflates and aryl
triflates were the most favoured substrates in palladium-catalysed
aminocarbonylation, recently, the corresponding iodo analogues,
i.e., the iodo-alkenes and iodo-aromatics, provided clean, high-
yielding synthetic procedure towards carboxamides.4 The homo-
geneous catalytic synthesis of unsaturated carboxamides or aryl
carboxamides with various structures has been published also in
our group.5,6
chemistry7–9 and in cross-coupling.10 Iodostyrenes possessing the
iodo substituent in the unsaturated side chain ((E)-b-iodostyrene and
a
-iodostyrene) are also known as reactive substrates in Stille cross-
coupling,11 and Heck-12 and Stille-coupling13 reactions, respectively.
It is worth noting that in spite of their lower reactivity, the more
easily available bromo analogues ((E)-
-bromostyrene19,20) were used preferentially in various transition
metal-catalysed reactions.
b
-bromostyrene14–18 and
a
Encouraged by the increasing importance of unsaturated carbox-
amides, we decided to investigate the possibility of extending
the scope of aminocarbonylation to a substrate possessing both
‘iodo-vinyl’ and iodo-aryl functionalities. Accordingly, a system-
atic investigation of the aminocarbonylation of 10,4-diiodostyr-
ene with simple primary and secondary amines, as well as with
amino acid methyl esters is reported here.
2. Results and discussion
2.1. Synthesis of 10,4-diiodostyrene (3)
The above diiodo substrate (3) has been synthesised according
to some analogous examples described in the seminal work of
Barton et al.21 Although the conventional ketone–hydrazone–iodo-
alkene route has been used, some modifications already published
for iodo-alkenes of similar structure have been carried out22 (see
Experimental). Accordingly, 4-iodoacetophenone (1) has been
converted to the corresponding hydrazone (2) by using barium
* Corresponding author.
´
E-mail address: kollar@ttk.pte.hu (L. Kollar).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.04.012

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A. Szilagyi et al. / Tetrahedron 65 (2009) 4484–4489
4485
oxide. Hydrazone 2 gave the target compound 3 in 81% yield upon
addition of iodine in the presence of a base (TMG¼N,N,N0,N’-tet-
ramethylguanidine) (Scheme 1). The last step had to be carried out
under argon providing strictly moisture- and oxygen-free condi-
tions. The diiodo substrate (3) must be kept under argon in a re-
frigerator protected from light. Under these conditions it can be
stored for months without any sign of decomposition.
formation of ‘tricarbonylated’ 6 at 40 bar CO pressure (compare
entries 1 and 2, 5 and 6, 7 and 8). While good to excellent yields
were obtained for 5, the yields of 6 fall typically below 20% except
for a (entry 2). Both types of compounds were isolated by column
chromatography. It is worth noting that aniline (b), the amine of the
lowest basicity in the series of amines used, resulted in sub-
stantially lower yields (entries 3 and 4) and the products could not
be isolated as highly pure compound for full characterisation.
Surprisingly, the application of amino acid ester hydrochlorides
(e–h) resulted in rather different product distribution. The mono-
carboxamide derivatives (4), i.e., those compounds containing an
unreacted iodo-arene functionality, were formed with high chemo-
selectivity at atmospheric carbon monoxide pressure (entries 9, 11,
13 and 15). The formation of dicarboxamide-type products (5) was
highly favoured towards 6 at high CO pressure (entries 10, 12 and
14). The carboxamide–ketocarboxamide products (6) were
obtained in low yields. Only 6f and 6h could be isolated as pure
products and fully characterised.
X
I
I2, TMG
I
I
X = O
3
(81 %)
1
2
N2H4, BaO
X = NNH2
Scheme 1. Synthesis of 3 from the corresponding ketone (1) via its hydrazone (2).
2.3. Aminocarbonylation of N-(methoxycarbonylmethyl)-2-
(4-iodo-phenyl)-acrylamide (4e)
2.2. Aminocarbonylation of 10,4-diiodostyrene (3)
The easy availability of 4-iodo-phenyl-acrylamides enabled the
synthesis of 7 and 8 containing different N-substituents in the
amide functionalities. The aminocarbonylation of 4e resulted in
almost exclusive formation of 8a, 8c and 8f (Scheme 3). These
target compounds were isolated in high yields (78–88%) and fully
characterised. The ‘mixed’ dicarboxamides (7a, 7c and 7f) were
formed only in traces (<5%) and could be detected by 1H and 13C
NMR only.
10,4-Diiodostyrene (3) was reacted with tert-butylamine (a),
aniline (b), piperidine (c), morpholine (d), methyl glycinate (e),
methyl alaninate (f), methyl valinate (g) and methyl prolinate (h).
All reactions were carried out both under atmospheric and under
high pressure (40 bar) carbon monoxide in the presence of in situ
generated palladium(0)-triphenylphosphine catalysts (Scheme 2).
Palladium(II) acetate was used as catalytic precursor and reduced to
Pd(0) as described previously in detail.23,24
2.4. Alkoxycarbonylation of 10,4-diiodostyrene (3)
O
O
O
10,4-Diiodostyrene (3) was also reacted with methanol under
high pressure (60 bar) carbon monoxide in the presence of in situ
palladium(0)-triphenylphosphine catalysts (Scheme 4). Complete
conversion but a low isolated yield of 23% for 9 was obtained. It is
worth noting that with other alcohols (benzyl alcohol, tert-butanol)
the isolation of the corresponding esters failed.
I
NR'R''
NR'R''
O
NR'R''
+
CO, HNR'R''
+
Pd(OAc)2 /PPh3
I
I
NR'R''
O
O
NR'R''
The low yields of esters could be explained by two side reactions
observed already for iodo-alkene derivatives. On one hand, some
carboxylic acid and anhydride formation was detected with low-
reactivity nucleophiles such as benzyl alcohol and especially tert-
butanol, due to the presence of traces of H2O in the solvent and
adsorbed on the wall of the glassware.26 Thus, hydroxy-
carbonylation instead of alkoxycarbonylation might take place. On
the other hand, the iodo-alkene functionality of 3 underwent hy-
drolysis under the severe reaction conditions, resulting in the
starting acetophenone derivative (1) via its enol form.
3
4
5
6
R'
H
H
R''
t-Bu
Ph
a
b
c
d
e
f
-(CH2)5-
-(CH2)2O(CH2)2-
H
H
CH2COOCH3
CH(CH3)COOCH3
g
h
H
CH(CH(CH3)2)COOCH3
-CH(COOCH3)(CH2)3-
Scheme 2. Palladium-catalysed aminocarbonylation of 3.
3. Conclusions
In summary, amino- and alkoxycarbonylation of 10,4-diiodos-
tyrene, possessing two iodo substituents with different reactivity,
were carried out. Both types of palladium-catalysed carbonylations
The reactivity of the iodo-alkene moiety of 3, compared to cyclic6
and open-chain aliphatic iodo-alkenes,25 was found to be excep-
tionally high. This functionality was transferred to the corresponding
carboxamide functionality in all cases. In this way, 2-(4-iodo-phenyl)-
acrylamides (4), 2-(4-carboxamido-phenyl)-acrylamides (5) and 2-
(4-glyoxylamido-phenyl)-acrylamides (6) were formed depending
on the type of the amines and on the reaction conditions.
The mixture of 5 and 6 was obtained by using simple primary (a)
and secondary amines (c,d) even at atmospheric carbon monoxide
pressure. The dicarboxamide-type products (5) were formed as the
major ones under all reaction conditions and the yields of synthetic
importance were obtained especially with secondary amines (en-
tries 5–8). The reaction could be shifted slightly towards the
proved to be efficient method for the functionalisation of a-iodo-
vinyl and iodo-aryl functionalities. Dicarboxamide and carbox-
amide-ketocarboxamide derivatives were synthesised by using the
variety of amine nucleophiles. The arylacrylamide-type products
could serve as intermediates of chiral building blocks, such as 2-
aryl-propionic amides, available, e.g., via asymmetric hydrogena-
tion. Furthermore, the application of iodo-alkenes/iodo-arenes, as
synthetic surrogates of the corresponding enol-triflate/aryl triflate
analogues in palladium-catalysed carbonylations, is supported by
green chemistry principles such as high yields and selectivities
obtained in clean homogeneous catalytic reactions.

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A. Szilagyi et al. / Tetrahedron 65 (2009) 4484–4489
O
O
O
NH
COOCH3
NH
COOCH3
+
NH
O
COOCH3
40 bar CO, HNR'R"
Pd(OAc)2 / PPh3
I
NR'R''
O
O
NR'R''
4e
7
8
R'
H
R''
(88 %)
(82 %)
(78 %)
a
c
t-Bu
-(CH2)5-
f
H
CH(CH3)COOCH3
Scheme 3. Palladium-catalysed aminocarbonylation of 4e.
COOMe
I
NaHCO3 (2ꢁ50 mL), water (50 mL), saturated aqueous Na2S2O3
(10 mL) and water (3ꢁ50 mL) again, dried over sodium sulfate and
evaporated. The iodo-alkene (3) was obtained as a red-brown vis-
cous material and used for carbonylation experiments without
further purification.
60 bar CO, MeOH
Pd(OAc)2 / PPh3
I
COOMe
9 (23 %)
3
4.2.1. 10,4-Diiodostyrene (3)
Scheme 4. Palladium-catalysed alkoxycarbonylation of 3.
dH (400 MHz, CDCl3) 7.62 (d, 8.1 Hz, 2H, Ph), 7.23 (d, 8.1 Hz, 2H,
Ph), 6.45 (br s, 1H, ]CH), 6.07 (br s, 1H, ]CH). dC (100.6 MHz,
CDCl3) 141.3, 137.3, 129.8, 127.9, 105.9, 94.8. IR (KBr, cmꢂ1): 1602
(C]C). MS m/z (rel int. %): 356 (22), 229 (100), 102 (47). Analysis
calculated for C8H6I2 (355.94): C, 27.00; H, 1.70. Found: C, 27.22; H,
1.86. Rf (petroleum ether (40–70)) 0.58; brown viscous material.
Yield: 10.02 g, 81%.
4. Experimental
4.1. General procedures
1H and 13C NMR spectra were recorded in CDCl3 on a Varian
Inova 400 spectrometer at 400.13 MHz and 100.62 MHz, re-
spectively. Chemical shifts
d are reported in parts per million rela-
4.3. Aminocarbonylation of 3 at normal pressure
tive to residual CHCl3 (7.26 and 77.00 ppm for 1H and 13C,
respectively). Elemental analyses were measured on a 1108 Carlo
Erba apparatus. Samples of the catalytic reactions were analysed
with a Hewlett Packard 5830A gas chromatograph fitted with
a capillary column coated with OV-1. TLC analyses were carried out
with Merck TLC sheets (Silica gel 60 F254) and chloroform/ethyl
acetate or dichloromethane/ethyl acetate mixtures as appropriate
eluents.
In a typical experiment Pd(OAc)2 (5.6 mg, 0.025 mmol), PPh3
(13.1 mg, 0.05 mmol), 0.5 mmol diiodo substrate (3), and 3.0 mmol
non-functionalized amine (a–d) (or 1.1 mmol amino acid methyl
ester (e–h) hydrochloride) were dissolved in 10 mL of DMF under
argon. Triethylamine (0.5 mL) was added to the homogeneous
yellow solution and the atmosphere was changed to carbon mon-
oxide. The colour changed to dark red. The reaction was conducted
for a given reaction time (see Table 1) at 50 ꢀC. Some metallic
palladium was formed and precipitated at the end of the reaction,
which was filtered off. (A sample of this solution was immediately
analysed by GC–MS and TLC.) The mixture was then concentrated
and evaporated to dryness. The residue was dissolved in chloroform
(20 mL) and washed in turn with water (20 mL). The organic phase
was thoroughly washed with 5% HCl (2ꢁ20 mL), saturated NaHCO3
(20 mL), brine (20 mL), dried over Na2SO4 and concentrated to
a yellow waxy material or a thick oil. The chemically pure products
(2-(4-iodo-phenyl)-acrylamides (4), 2-(4-carboxamido-phenyl)-
acrylamides (5), 2-(4-glyoxylamido-phenyl)-acrylamides (6)) were
isolated from the reaction mixtures by column chromatography
(silica, chloroform/ethyl acetate or dichloromethane/ethyl acetate
mixtures) yielding the desired compounds typically as yellow
solids.
4.2. Synthesis of 10,4-diiodostyrene (3)
4-Iodoacetophenone (1) (10.01 g, 40.7 mmol), freshly distilled
hydrazine hydrate (98%, 2.24 g, 44.8 mmol) and barium oxide (1.63 g)
in absolute ethanol (50 mL) were heated for 3 days at 90 ꢀC. After
completion of the reaction, iced water (200 mL) and dichloro-
methane (130 mL) were added, and the white precipitate was fil-
tered. The organic phase was separated and dried over sodium sulfate
for 1 day. (It is worth noting that the hydrazone derivative can be
stored over sodium sulfate for several days without decomposition.)
At last it was evaporated to give the hydrazone (2) derivative. The
product was used in the next step without further purification.
To a stirred solution of iodine (18.19 g, 71.7 mmol) in dichloro-
methane (50 mL) the mixture of 1,1,3,3-tetramethylguanidine
(TMG, 11.96 g, 103.8 mmol) and 4-iodoacetophenone hydrazone (2)
(9 g, 34.6 mmol) in dichloromethane (30 mL) was added dropwise
between 0 and 12 ꢀC, cooled in an iced-water bath during the ad-
dition. After the addition was complete, the mixture was stirred for
half an hour. Then the solvent was evaporated and the residue was
heated at 90 ꢀC under argon atmosphere for 2 h. The mixture was
poured into water (300 mL) and extracted with dichloromethane
(4ꢁ50 mL). The combined organic layer was washed successively
with 1 N aqueous HCl (3ꢁ50 mL), water (50 mL), 5% aqueous
4.4. Aminocarbonylation of 3 at high pressure
The DMF solution of the catalyst precursor and reactants
(amounts as given above) was transferred under argon into
a 100 mL stainless steel autoclave. The reaction vessel was pres-
surised up to 40 bar total pressure with carbon monoxide and the
magnetically stirred mixture was heated in an oil bath at 50 ꢀC for
22 h. The work-up procedure is identical with that given above.

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A. Szilagyi et al. / Tetrahedron 65 (2009) 4484–4489
4487
NH), 1.45 (s, 9H, tBu), 1.34 (s, 9H, tBu). dC (100.6 MHz, CDCl3) 166.5,
166.3, 145.4, 139.9, 135.8, 127.9, 127.1, 121.2, 51.7, 51.6, 28.7, 28.6. IR
(KBr, cmꢂ1): 3301 (NH), 1661 (CON), 1644 (CON). MS m/z (rel int. %):
302 (44), 287 (26), 230 (100), 202 (35), 174 (23), 102 (30). Analysis
calculated for C18H26N2O2 (302.42): C, 71.49; H, 8.67; N, 9.26.
Found: C, 71.25, H, 8.82; N, 9.01; Rf (50% EtOAc/CHCl3) 0.67; off-
white, mp 173–176 ꢀC. Yield: 83 mg, 55%.
Table 1
Palladium-catalysed aminocarbonylation of 10,4-diiodostyrene (3)a
Entry Amine
Retention p(CO) Composition of the reaction
time (h)
(bar)
mixture (%)b (isolated yield, %)
4
5
6
1
2
3
4
5
6
7
8
tBuNH2 (a)
24
24
90
90
24
24
1
40
1
40
1
40
1
40
1
40
1
40
1
40
1
40
0
0
71 (55)
51 (42)
31 (n.d.)
30 (n.d.)
95 (84)
80 (72)
96 (88)
92 (86)
<2
68 (56)
<2
70 (64)
15 (n.d.)
78 (61)
<2
29 (n.d.)c
49 (40)
4 (n.d.)
32 (n.d.)
5 (n.d.)
20 (16)
4 (n.d.)
8 (6)
<2
<2
0
28 (20)
0
20 (n.d.)
tBuNH2 (a)
Aniline (b)
Aniline (b)
Piperidine (c)
Piperidine (c)
Morpholine (d) 45
Morpholine (d) 45
GlyOMe (e)
GlyOMe (e)
AlaOMe (f)
AlaOMe (f)
ValOMe (g)
ValOMe (g)
ProOMe (h)
ProOMe (h)
4.7.2. 2-(4-N-tert-Butylglyoxylamido-phenyl)-N-tert-butyl-
acrylamide (6a)
0
0
0
dH (400 MHz, CDCl3) 8.32 (d, 8.3 Hz, 2H, Ar), 7.47 (d, 8.3 Hz,
2H, Ar), 6.95 (br s, 1H, NH), 6.03 (br s, 1H, ]CH), 5.65 (br s, 1H,
t
t
9
24
24
24
24
24
24
24
24
>96 (89)
30 (n.d.)
>98 (90)
<2
85 (77)
<2
]CH), 5.47 (br s, 1H, NH), 1.44 (s, 9H, Bu), 1.37 (s, 9H, Bu). dC
(100.6 MHz, CDCl3) 187.8, 166.2, 160.9, 145.3, 142.7, 133.1, 131.5,
127.7, 121.9, 51.7, 51.6, 28.6, 28.3. IR (KBr, cmꢂ1): 3289 (NH), 1679
(CO), 1659 (CON), 1644 (CON), 1604 (C]C). MS m/z (rel int. %):
330 (1), 230 (100), 203 (58), 102 (22). Analysis calculated for
C19H26N2O3 (330.43): C, 69.06; H, 7.93; N, 8.48. Found: C, 68.85;
H, 8.12; N, 8.19; Rf (33% EtOAc/CH2Cl2) 0.85; pale-yellow, mp 138–
142 ꢀC. Yield: 40 mg, 66%.
10
11
12
13
14
15
16
>98 (90)
0
60 (55)
40 (31)
a
Reaction conditions: 0.025 mmol Pd(OAc)2, 0.05 mmol PPh3, 1 mmol 10,4-
diiodo-styrene (3), 3 mmol non-functionalised amine (or 1.1 mmol amino acid
methyl ester hydrochloride), 10 mL DMF.
b
4.7.3. 2-(4-N-Phenylcarboxamido-phenyl)-N-phenyl-
acrylamide (5b)
Practically complete conversion (>98%) has been obtained in all cases except for
aniline (35% and 62% at 1 bar and 40 bar CO pressure, respectively).
c
n.d.¼not determined (not isolated as pure products in the given run).
dH (400 MHz, CDCl3) 7.95 (d, 8.2 Hz, 2H, Ar), 7.72 (d, 7.3 Hz, 2H,
o-Ph), 7.68 (d, 7.3 Hz, 2H, o-Ph), 7.58 (d, 8.2 Hz, 2H, Ar), 7.02 (t,
7.3 Hz, 2H, p-Ph), 6.90 (t, 7.3 Hz, 4H, m-Ph), 5.93 (br s, 1H, ]CH),
5.86 (br s, 1H, ]CH). IR (KBr, cmꢂ1): 3329 (NH), 1650 (CON), 1597
(C]C).
4.5. Aminocarbonylation of 4e at high pressure
In a typical experiment Pd(OAc)2 (5.6 mg, 0.025 mmol), PPh3
(13.1 mg, 0.05 mmol), 0.5 mmol iodoaromatic substrate (4e),
1.5 mmol non-functionalized amine (a or c) (or 0.55 mmol alanine
methyl ester (f)) were dissolved in 10 mL of DMF under argon.
Triethylamine (0.5 mL) was added to the homogeneous yellow so-
lution and this mixture was transferred under argon into a 100 mL
stainless steel autoclave. The reaction vessel was pressurised to
40 bar total pressure with carbon monoxide and the magnetically
stirred mixture was heated in an oil bath at 50 ꢀC for 24 h. Some
metallic palladium was formed and precipitated at the end of the
reaction, which was filtered off. (A sample of this solution was im-
mediately analysed by GC–MS and TLC.) The mixture was then
concentrated and evaporated to dryness. The residue was dissolved
in chloroform (20 mL) and washed in turn with water (20 mL). The
organic phase was thoroughly washed with 5% HCl (2ꢁ20 mL), sat-
urated NaHCO3 (20 mL), brine (20 mL), dried over Na2SO4 and con-
centrated to a yellow waxy material or a thick oil. The chemically
pure products (8) were isolated from the reaction mixtures by col-
umn chromatography (silica, dichloromethane/ethyl acetate 1/1).
4.7.4. 2-(4-N-Phenylglyoxylamido-phenyl)-N-phenyl-
acrylamide (6b)
dH (400 MHz, CDCl3) 7.10–7.92 (m, 14H, Ar), 6.65 (br s, 2H, NH),
6.26 (br s, 1H, ]CH), 5.83 (br s, 1H, ]CH).
4.7.5. 2-(4-N,N-Pentan-1,5-diyl-carboxamido-phenyl)-N,N-pentan-
1,5-diyl-acrylamide (5c)
dH (400 MHz, CDCl3) 7.42 (d, 8.3 Hz, 2H, Ar), 7.32 (d, 8.3 Hz, 2H,
Ar), 5.71 (br s, 1H, ]CH), 5.34 (br s, 1H, ]CH), 3.65 (br s, 4H,
N(CH2)2), 3.30 (br s, 4H, N(CH2)2), 1.30–1.70 (m, 12H, 2ꢁ(CH2)3). dC
(100.6 MHz, CDCl3) 169.7, 168.8, 144.5, 136.7, 136.5, 127.3, 125.7,
114.1, 49.0 (br), 48.0, 43.2 (br), 42.4, 26.4, 25.6, 24.5, 24.4. IR (KBr,
cmꢂ1): 1677 (CON), 1635 (CON). MS m/z (rel int. %): 326 (55), 325
(100), 282 (9), 242 (41), 215 (22), 102 (21). Analysis calculated for
C20H26N2O2 (326.44): C, 73.59; H, 8.03; N, 8.58. Found: C, 73.65; H,
8.22; N, 8.44. Rf (50% EtOAc/CHCl3) 0.45; pale-brown highly viscous
material. Yield: 138 mg, 84%.
4.7.6. 2-(4-N,N-Pentan-1,5-diyl-glyoxylamido-phenyl)-N,N-
pentan-1,5-diyl-acrylamide (6c)
4.6. Alkoxycarbonylation of 3 at high pressure
dH (400 MHz, CDCl3) 7.88 (d, 8.3 Hz, 2H, Ar), 7.50 (d, 8.3 Hz, 2H,
Ar), 5.80 (br s, 1H, ]CH), 5.42 (br s, 1H, ]CH), 3.63 (br s, 4H,
N(CH2)2), 3.25 (br s, 4H, N(CH2)2), 1.40–1.70 (m, 12H, 2ꢁ(CH2)3). dC
(100.6 MHz, CDCl3) 191.1, 168.2, 165.2, 144.2, 141.6, 133.0, 130.1,
126.3, 116.4, 48.0, 47.1, 42.2, 41.7, 26.4, 26.2, 25.4, 25.3, 24.4, 24.3. IR
(KBr, cmꢂ1): 1678 (CO), 1638 (br, CON). Analysis calculated for
C21H26N2O3 (354.45): C, 71.16; H, 7.39; N, 7.90. Found: C, 71.02; H,
7.42; N, 7.72. Rf (50% EtOAc/CHCl3) 0.60; brown viscous material.
Yield: 29 mg, 16%.
A mixture of 3 (398 mg, 1 mmol), palladium(II) acetate (5.6 mg,
0.025 mmol), and PPh3 (13.1 mg, 0.05 mmol) was dissolved in 10 mL
of DMF (or, in parallel experiments, 20 mL of methyl ethyl ketone)
under argon, and NEt3 (0.5 mL) and methanol (0.13 mL, 5 mmol) as
O-nucleophile were added. The reaction mixture was then trans-
ferred under argon into a 100 mL stainless steel autoclave, which
was pressurised to 60 bar with CO and the magnetically stirred
mixture was heated in an oil bath at 50 ꢀC for 70 h. The work-up
procedure was identical with that given above for the carboxamides.
4.7.7. 2-(4-N,N-3-Oxapentan-1,5-diyl-carboxamido-phenyl)-N,N-
3-oxapentan-1,5-diyl-acrylamide (5d)
4.7. Characterisation of the products
dH (400 MHz, CDCl3) 7.45 (d, 8.2 Hz, 2H, Ar), 7.36 (d, 8.2 Hz, 2H,
Ar), 5.78 (br s, 1H, ]CH), 5.39 (br s, 1H, ]CH), 3.30–3.76 (m, 16H,
2ꢁ(CH2)2O(CH2)2). dC (100.6 MHz, CDCl3) 169.7, 168.8, 143.5, 136.8,
135.5, 127.7, 125.8, 115.6, 66.7 (2C), 47.3 (br), 41.9 (br). IR (KBr,
cmꢂ1): 1636 (br, 2ꢁCON). MS m/z (rel int. %): 330 (38), 329 (36), 244
4.7.1. 2-(4-N-tert-Butylcarboxamido-phenyl)-N-tert-butyl-
acrylamide (5a)
dH (400 MHz, CDCl3) 7.70 (d, 8.3 Hz, 2H, Ar), 7.39 (d, 8.3 Hz, 2H,
Ar), 5.98 (br s, 2H, ]CHþNH), 5.56 (br s, 1H, ]CH), 5.48 (br s, 1H,

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A. Szilagyi et al. / Tetrahedron 65 (2009) 4484–4489
4488
(100), 217 (16), 159 (37), 102 (41). Analysis calculated for
C18H22N2O4 (330.38): C, 65.44; H, 6.71; N, 8.48. Found: C, 65.30; H,
6.88; N, 8.26. Rf (3% EtOH/CH2Cl2) 0.48; highly viscous yellow ma-
terial. Yield: 146 mg, 88%.
4.7.13. 2-(4-N-(1-Methoxycarbonylethyl)-glyoxylamido-phenyl)-
N-(1-methoxycarbonylethyl)-acrylamide (6f)
dH (400 MHz, CDCl3) 8.33 (d, 8.3 Hz, 2H, Ar), 7.52 (d, 8.3 Hz, 2H,
Ar), 6.23 (br s, 2H, NH), 6.13 (br s, 1H, ]CH), 5.75 (br s, 1H, ]CH),
4.60–4.73 (m, 2H, CHCOO), 3.77 (s, 3H, OCH3), 3.73 (s, 3H, OCH3),
1.49 (d, 7.3 Hz, 3H, CHCH3), 1.42 (d, 7.3 Hz, 3H, CHCH3). dC
(100.6 MHz, CDCl3) 186.2, 173.1, 172.3, 166.5, 166.2, 142.4, 133.0,
131.5, 128.0, 127.3, 123.5, 52.6, 52.5, 48.4, 48.1, 18.1, 18.0. IR (KBr,
cmꢂ1): 3282 (NH), 1742 (COO), 1660 (CO), 1647 (CON), 1608 (C]C).
Analysis calculated for C19H22N2O7 (390.39): C, 58.46; H, 5.68; N,
7.18; Found: C, 58.28; H, 5.56; N, 5.41. Rf (50% EtOAc/CH2Cl2) 0.67;
brown highly viscous solid. Yield: 39 mg, 20%.
4.7.8. 2-(4-N,N-3-Oxapentan-1,5-diyl-glyoxylamido-phenyl)-N,N-
3-oxapentan-1,5-diyl-acrylamide (6d)
dH (400 MHz, CDCl3) 7.90 (d, 8.1 Hz, 2H, Ar), 7.52 (d, 8.1 Hz, 2H,
Ar), 5.73 (br s, 1H, ]CH), 5.49 (br s, 1H, ]CH), 3.25–3.75 (m, 16H,
2ꢁ(CH2)2O(CH2)2). dC (100.6 MHz, CDCl3) 190.4, 168.6, 165.3, 143.5,
141.7, 133.2, 130.5, 126.5, 117.9, 67.0 (2C), 66.9 (2C), 47.6, 46.5, 42.2,
41.9. IR (KBr, cmꢂ1): 1675 (CO), 1630 (CON). Analysis calculated for
C19H22N2O5 (358.39): C, 63.68; H, 6.19; N, 7.82. Found: C, 63.50; H,
6.02; N, 7.55. Rf (3% EtOAc/CH2Cl2) 0.47; off-white crystals, mp 135–
140 ꢀC. Yield: 11 mg, 6%.
4.7.14. 2-(4-Iodo-phenyl)-N-(1-methoxycarbonyl-2-methylpropyl)-
acrylamide (4g)
dH (400 MHz, CDCl3) 7.69 (d, 8.4 Hz, 2H, Ar), 7.13 (d, 8.4 Hz, 2H,
Ar), 6.15 (br s, 1H, NH), 6.02 (br s, 1H, ]CH), 5.63 (br s, 1H, ]CH),
4.59–4.64 (m, 1H, CHCOO), 3.72 (s, 3H, OCH3), 0.92 (d, 6.5 Hz, 3H,
CHCH3), 0.84 (d, 6.5 Hz, 3H, CHCH3). dC (100.6 MHz, CDCl3) 172.3,
166.9, 143.8, 137.8, 136.0, 129.7, 122.2, 94.6, 57.4, 52.2, 31.2, 19.1, 17.8.
IR (KBr, cmꢂ1): 3301 (NH), 1744 (COO), 1645 (CON). MS m/z (rel int.
%): 387 (9), 328 (51), 273 (53), 229 (100), 102 (67). Analysis calcu-
lated for C15H18NO3I (387.22): C, 46.53; H, 4.69; N, 3.62. Found: C,
46.39; H, 4.77; N, 3.40. Rf (40% EtOAc/CHCl3) 0.87; pale-brown solid,
mp 60–64 ꢀC. Yield: 148 mg, 77%.
4.7.9. 2-(4-Iodo-phenyl)-N-methoxycarbonylmethyl-
acrylamide (4e)
dH (400 MHz, CDCl3) 7.69 (d, 8.3 Hz, 2H, Ar), 7.14 (d, 8.3 Hz, 2H,
Ar), 6.28 (br s, 1H, NH), 6.07 (br s, 1H, ]CH), 5.66 (br s, 1H, ]CH),
4.09 (d, 5.4 Hz, 2H, CH2COO), 3.73 (s, 3H, OCH3). dC (100.6 MHz,
CDCl3) 170.1, 167.2, 143.5, 137.8, 136.0, 129.8, 122.5, 94.6, 52.4, 41.5.
IR (KBr, cmꢂ1): 3295 (NH), 1754 (COO), 1644 (CON). MS m/z (rel int.
%): 345 (43), 257 (32), 229 (100), 159 (16), 102 (76). Analysis cal-
culated for C12H12NO3 (345.14): C, 41.76; H, 3.50; N, 4.06. Found: C,
41.51; H, 3.39; N, 3.86. Rf (20% EtOAc/CHCl3) 0.56; off-white solid,
mp 90–92 ꢀC. Yield: 154 mg, 89%.
4.7.15. 2-(4-N-(1-Methoxycarbonyl-2-methylpropyl)-
carboxamido-phenyl)-N-(1-methoxycarbonyl-2-methylpropyl)-
acrylamide (5g)
4.7.10. 2-(4-N-(Methoxycarbonylmethyl)-carboxamido-phenyl)-N-
methoxycarbonylmethyl-acrylamide (5e)
dH (400 MHz, CDCl3) 7.81 (d, 8.1 Hz, 2H, Ar), 7.50 (d, 8.1 Hz, 2H,
Ar), 6.66 (br d, 8.5 Hz, 1H, NH), 6.18 (br d, 8.5 Hz, 1H, NH), 6.12 (br s,
1H, ]CH), 5.72 (br s, 1H, ]CH), 4.76–4.79 (m, 1H, CHCOO), 4.63–
4.67 (m, 1H, CHCOO), 3.75 (s, 3H, OCH3), 3.72 (s, 3H, OCH3), 2.15–
2.30 (m, 2H, 2ꢁCH(CH3)2), 1.01 (d, 6.9 Hz, 3H, CH(CH3)), 0.99 (d,
6.9 Hz, 3H, CH(CH3)), 0.93 (d, 6.9 Hz, 3H, CH(CH3)), 0.84 (d, 6.9 Hz,
3H, CH(CH3)). dC (100.6 MHz, CDCl3) 172.6, 172.2, 166.9, 166.7, 143.9,
139.9, 134.2, 128.2, 127.5, 123.0, 57.5, 57.4, 52.2 (2C), 31.6, 31.2, 19.1,
19.0, 18.0, 17.8. IR (KBr, cmꢂ1): 3277 (NH), 1744 (COO), 1646 (CON).
Analysis calculated for C22H30N2O6 (418.49): C, 63.14; H, 7.23; N,
6.69. Found: C, 63.25; H, 7.37; N, 6.50. Rf (40% EtOAc/CHCl3) 0.57;
brown viscous solid. Yield: 128 mg, 61%.
dH (400 MHz, CDCl3) 7.71 (d, 8.3 Hz, 2H, Ar), 7.38 (d, 8.3 Hz, 2H,
Ar), 7.18 (br s, 1H, NH), 6.61 (br s, 1H, NH), 6.03 (br s, 1H, ]CH), 5.65
(br s, 1H, ]CH), 4.12 (d, 5.6 Hz, 2H, CH2COO), 4.06 (d, 5.6 Hz, 2H,
CH2COO), 3.72 (s, 3H, CH3), 3.70 (s, 3H, CH3). dC (100.6 MHz, CDCl3)
170.4, 170.1, 167.6, 167.0, 143.5, 139.7, 133.4, 128.0, 127.5, 122.6, 52.3,
52.2, 41.6, 41.4. IR (KBr, cmꢂ1): 1751 (COO), 1662 (br, CON). Analysis
calculated for C16H18N2O6 (334.33): C, 57.48; H, 5.43; N, 8.38.
Found: C, 57.40; H, 5.32; N, 8.19. Rf (40% EtOAc/CH2Cl2) 0.25; highly
viscous yellow material. Yield: 94 mg, 56%.
4.7.11. 2-(4-Iodo-phenyl)-N-(1-methoxycarbonylethyl)-
acrylamide (4f)
dH (400 MHz, CDCl3) 7.67 (d, 8.4 Hz, 2H, Ar), 7.11 (d, 8.4 Hz, 2H,
Ar), 6.30 (br s, 1H, NH), 6.01 (br s, 1H, ]CH), 5.62 (br s, 1H, ]CH),
4.61 (quint., 7.2 Hz, 1H, CHCOO), 3.70 (s, 3H, OCH3), 1.39 (d, 7.3 Hz,
3H, CHCH3). dC (100.6 MHz, CDCl3) 173.2, 166.6, 143.7, 137.8, 136.0,
129.8, 122.1, 94.6, 52.5, 48.4, 18.2. IR (KBr, cmꢂ1): 3275 (NH), 1745
(COO), 1646 (CON). MS m/z (rel int. %): 359 (17), 300 (80), 257 (38),
229 (100), 102 (71). Analysis calculated for C13H14NO3I (359.16): C,
43.47; H, 3.93; N, 3.90. Found: C, 43.28; H, 4.10; N, 3.77. Rf (10%
EtOAc/CHCl3) 0.52; pale-brown solid, mp 73–77 ꢀC. Yield: 162 mg,
90%.
4.7.16. 2-(4-Iodo-phenyl)-N,N-(1-methoxycarbonyl-1,4-
butanediyl)-acrylamide (4h)
dH (400 MHz, CDCl3) 7.62 (d, 7.8 Hz, 2H, Ar), 7.21 (d, 7.8 Hz, 2H,
Ar), 5.71 (br s, 1H, ]CH), 5.42 (br s, 1H, ]CH), 4.60–4.54 (m, 1H,
CHCOO), 3.72 (s, 3H, OCH3), 3.26–3.30 (m, 2H, CH2), 0.76–1.22 (m,
4H, CH2CH2). dC (100.6 MHz, CDCl3) 172.4, 168.7, 144.5, 137.9, 134.8,
127.9, 115.8, 94.4, 58.4, 52.3, 48.6, 29.4, 24.8. IR (KBr, cmꢂ1): 1744
(COO), 1639 (CON). MS m/z (rel int. %): 385 (17), 326 (91), 257 (33),
229 (100), 102 (66). Analysis calculated for C15H16NO3I (385.20): C,
46.77; H, 4.19; N, 3.64. Found: C, 46.60; H, 4.01; N, 3.40. Rf (10%
EtOAc/CHCl3) 0.50; red-brown highly viscous solid. Yield: 173 mg,
90%.
4.7.12. 2-(4-N-(1-Methoxycarbonylethyl)-carboxamido-phenyl)-N-
(1-methoxycarbonylethyl)-acrylamide (5f)
dH (400 MHz, CDCl3) 7.78 (d, 8.2 Hz, 2H, Ar), 7.42 (d, 8.2 Hz, 2H,
Ar), 7.00 (br d, 6.8 Hz, 1H, NH), 6.41 (br d, 6.8 Hz, 1H, NH), 6.07 (br s,
1H, ]CH), 5.67 (br s, 1H, ]CH), 4.75 (quint., 7.2 Hz, 1H, CHCOO),
4.64 (quint., 7.2 Hz, 1H, CHCOO), 3.75 (s, 3H, OCH3), 3.71 (s, 3H,
OCH3), 1.49 (d, 7.3 Hz, 3H, CHCH3), 1.40 (d, 7.3 Hz, 3H, CHCH3). dC
(100.6 MHz, CDCl3) 173.6, 173.2, 166.6, 166.3, 143.7, 139.7, 133.8,
128.1, 127.4, 122.7, 52.5, 52.4, 48.5, 48.3, 18.3, 18.0. IR (KBr, cmꢂ1):
3365 (NH), 1745 (COO), 1646 (br, 2ꢁCON), 1611 (C]C). Analysis
calculated for C18H22N2O6 (362.38): C, 59.66; H, 6.12; N, 7.73.
Found: C, 59.50; H, 6.01; N, 7.48. Rf (50% EtOAc/CH2Cl2) 0.45; brown
highly viscous solid. Yield: 117 mg, 64%.
4.7.17. 2-(4-N,N-(1-Methoxycarbonyl-1,4-butanediyl)-
carboxamido-phenyl)-N,N-(1-methoxycarbonyl-1,4-butanediyl)-
acrylamide (5h)
dH (400 MHz, CDCl3) 7.50 (br s, 4H, Ar), 5.76 (br s, 1H, ]CH), 5.47
(br s, 1H, ]CH), 4.50–4.63 (m, 2H, 2ꢁCHCOO), 3.70 (s, 3H, OCH3),
3.68 (s, 3H, OCH3), 3.20–3.65 (m, 4H, 2ꢁNCH2), 1.70–2.25 (m, 8H,
2ꢁCH2CH2). dC (100.6 MHz, CDCl3) 172.6, 172.4, 168.9, 168.8, 144.7,
137.1, 136.0, 127.9, 125.9, 116.4, 59.1, 58.5, 52.2 (2C), 49.9, 48.6, 29.4,
29.3, 25.4, 24.8. IR (KBr, cmꢂ1): 1744 (COO), 1638 (CON). MS m/z (rel
int. %): 414 (3), 355 (34), 286 (100), 258 (24), 102 (29). Analysis
calculated for C22H26N2O6 (414.46): C, 63.76; H, 6.32; N, 6.76.

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A. Szilagyi et al. / Tetrahedron 65 (2009) 4484–4489
4489
Found: C, 63.55; H, 6.42; N, 6.53. Rf (50% EtOAc/CHCl3) 0.26; golden
Rf (50% EtOAc/CH2Cl2) 0.51; pale-brown, mp 207–210 ꢀC (decom-
highly viscous solid. Yield: 114 mg, 55%.
posed). Yield: 146 mg, 78%.
4.7.18. 2-(4-N,N-(1-Methoxycarbonyl-1,4-butanediyl)-
glyoxylamido-phenyl)-N,N-(1-methoxycarbonyl-1,4-
butanediyl)-acrylamide (6h)
4.7.22. Methyl 2-(4-methoxycarbonylphenyl)-acrylate (9)
dH (400 MHz, CDCl3) 8.00 (d, 7.8 Hz, 2H, Ar), 7.47 (d, 7.8 Hz, 2H,
Ar), 6.43 (br s, 1H, ]CH), 5.95 (br s, 1H, ]CH), 3.92 (s, 3H, OCH3),
3.81 (s, 3H, OCH3). IR (KBr, cmꢂ1): 1725 (COO), 1609 (C]C). MS m/z
(rel int. %): 220 (48), 189 (100), 181 (47), 129 (13), 102 (23). Analysis
calculated for C12H12O4 (220.22): C, 65.45; H, 5.49. Found: C, 65.28;
H, 5.59. Rf (2% EtOAc/CHCl3) 0.80; pale-yellow viscous material.
Yield: 26 mg, 23%.
dH (400 MHz, CDCl3) 8.03 (d, 7.8 Hz, 2H, Ar), 7.63 (d, 7.8 Hz, 2H,
Ar), 5.88 (br s, 1H, ]CH), 5.62 (br s, 1H, ]CH), 4.56–4.70 (m, 2H,
CHCOO), 3.77 (s, 3H, OCH3), 3.74 (s, 3H, OCH3), 3.30–3.60 (m, 4H,
2ꢁNCH2), 1.80–2.35 (m, 8H, 2ꢁCH2CH2). dC (100.6 MHz, CDCl3)
190.4,172.3,171.8,168.4,165.1,144.6,141.3,132.6,132.0,126.6,118.2,
58.5, 58.3, 52.5, 52.3, 48.6, 47.2, 29.4, 29.1, 24.8, 24.6. IR (KBr, cmꢂ1):
1752 (COO),1681 (CO), 1646 (CON), 1604 (C]C). Analysis calculated
for C23H26N2O7 (442.47): C, 62.43; H, 5.92; N, 6.33. Found: C, 62.57;
H, 5.80; N, 6.18. Rf (50% EtOAc/CHCl3) 0.38; golden highly viscous
solid. Yield: 68 mg, 31%.
Acknowledgements
The authors thank the Hungarian Research Fund (OTKA
NI61591), the Joint Project of the European UniondHungarian
National Development Program (GVOP-3.2.1-2004-04-0168/3) for
the financial support and Johnson Matthey for the generous gift of
palladium(II) acetate.
4.7.19. 2-(4-(N-tert-Butylglyoxylamido)-phenyl)-N-
(methoxycarbonylmethyl)-acrylamide (8a)
dH (400 MHz, CDCl3) 8.32 (d, 8.3 Hz, 2H, Ar), 7.53 (d, 8.3 Hz, 2H,
Ar), 6.93 (br s, 1H, NH), 6.24 (br s, 1H, NH), 6.19 (br s, 1H, ]CH), 5.77
(br s,1H, ]CH), 4.10 (d, 5.4 Hz, 2H, CH2COO), 3.74 (s, 3H, OCH3),1.45
References and notes
t
(s, 9H, Bu). dC (100.6 MHz, CDCl3) 187.8, 170.0, 166.9, 160.9, 143.5,
´
1. Skoda-Fo¨ldes, R.; Kollar, L. Curr. Org. Chem. 2002, 6, 1097–1119.
142.0, 133.3, 131.5, 127.9, 123.7, 52.3, 51.7, 41.5, 28.3. IR (KBr, cmꢂ1):
3358 (NH), 1751 (COO), 1666 (br, 2ꢁCON), 1604 (C]C). Analysis
calculated for C18H21N2O5 (345.38): C, 62.60; H, 6.13; N, 8.11. Found:
C, 62.73; H, 6.30; N, 7.90. Rf (50% EtOAc/CH2Cl2) 0.67; yellow solid,
mp 69–73 ꢀC. Yield: 153 mg, 88%.
2. Applied Homogeneous Catalysis with Organometallic Compounds; Cornils, B., Herr-
mann, W. A., Eds.; Wiley-VCH: Weinheim, 1996; Transition Metals for Organic
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5. Acs, P.; Mu¨ller, E.; Rangits, G.; Lo´ ra´nd, T.; Kolla´r, L. Tetrahedron 2006, 62, 12051–
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(methoxycarbonylmethyl)-acrylamide (8c)
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dH (400 MHz, CDCl3) 7.91 (d, 8.2 Hz, 2H, Ar), 7.55 (d, 8.2 Hz, 2H,
Ar), 6.41 (br s, 1H, NH), 6.11 (br s, 1H, ]CH), 5.78 (br s, 1H, ]CH),
4.10 (d, 5.5 Hz, 2H, CH2COO), 3.74 (s, 3H, OCH3), 3.20–3.70 (m, 4H,
2ꢁNCH2), 1.50–1.70 (m, 6H, 3ꢁCH2). dC (100.6 MHz, CDCl3) 191.0,
170.0, 167.0, 165.1, 143.5, 142.5, 133.0, 129.8, 128.5, 123.3, 52.3, 47.0,
41.4, 26.3, 26.1, 24.3. IR (KBr, cmꢂ1): 3422 (NH), 1753 (COO), 1676
(CO), 1640 (br, 2ꢁCON). Analysis calculated for C18H20N2O5
(344.37): C, 62.78; H, 5.85; N, 8.13. Found: C, 62.61; H, 5.72; N, 7.88.
Rf (50% EtOAc/CH2Cl2) 0.50; pale-brown viscous material. Yield:
142 mg, 82%.
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8. Camps, M.; Jebri, A. Eur. Polym. J. 1994, 30, 1029–1035.
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4.7.21. 2-(4-(N-1-Methoxycarbonylethyl-glyoxylamido)-phenyl)-
N-(methoxycarbonylmethyl)-acrylamide (8f)
dH (400 MHz, CDCl3) 8.30 (d, 8.3 Hz, 2H, Ar), 7.49 (d, 8.3 Hz, 2H,
Ar), 6.26 (br s, 2H, 2ꢁNH), 6.15 (br s, 1H, ]CH), 5.76 (br s, 1H, ]CH),
4.62 (quint., 5.5 Hz, 2H, CHCOO), 3.74 (s, 3H, OCH3), 3.70 (s, 3H,
OCH3), 1.48 (d, 3H, CHCH3). dC (100.6 MHz, CDCl3) 186.5, 172.3,
170.0, 167.0, 161.0, 143.5, 133.0, 131.5, 128.5, 128.0, 123.7, 52.6, 52.3,
48.1, 41.4, 17.9. IR (KBr, cmꢂ1): 3355 (NH), 1747 (COO), 1716 (CO),
1667 (br, 2ꢁCON), 1605 (C]C). Analysis calculated for C18H20N2O7
(376.37): C, 57.44; H, 5.36; N, 7.44. Found: C, 57.31; H, 5.50; N, 7.17.
21. Barton, D. H. R.; Bashiardes, B.; Fourrey, J. L. Tetrahedron Lett. 1983, 24, 1605–
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1995, 14, 5605–5614 and references cited therein.
´
¨
´
24. Csakai, Z.; Skoda-Foldes, R.; Kollar, L. Inorg. Chim. Acta 1999, 286, 93–97.
´
25. Taka´cs, A.; Acs, P.; Farkas, R.; Kokotos, G.; Kolla´r, L. Tetrahedron 2008, 64, 9874–
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