Pd(0)/iodide salt-mediated Heck reaction of aryl nonaflates: Application to the synthesis of 2-(1-alkenyl)phenylphosphonates

Article abstract of DOI:10.1016/j.jfluchem.2011.06.029

Iodide salt, such as NaI, KI or n-Bu₄NI (TBAI), rather than bromide or chloride salt, was found to play a key role in the Pd(0)-catalyzed Heck reaction of aryl nonaflates and terminal alkenes. In the presence of PdCl₂(PPh₃)₂, NaI or TBAI in DMF, a class of 2-(1-alkenyl)phenylphosphonates was first synthesized via the reaction of o-phosphonylphenyl nonaflates with alkenes, the yields, regioselectivities and stereoselectivities were much dependent on the nature of the substituents. In case of the aryl nonaflates without bearing the sterically hindered phosphonyl group with the alkenes, the reactions proceeded more smoothly under the same conditions, leading to the linear products regioselectively in good to excellent yields. A rationale for this reaction is discussed.

Full text of DOI:10.1016/j.jfluchem.2011.06.029

Journal of Fluorine Chemistry 132 (2011) 982–986
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Journal of Fluorine Chemistry
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Short communication
Pd(0)/iodide salt-mediated Heck reaction of aryl nonaflates: Application to the
synthesis of 2-(1-alkenyl)phenylphosphonates
*
Ai-Yun Peng , Ba-Tian Chen, Zheng Wang, Bo Wang, Xiao-Bin Mo, Yuan-You Wang, Pei-Jiang Chen
School of Chemistry & Chemical Engineering, Sun Yat-sen University, 135 Xingangxi Lu, Guangzhou 510275, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Iodide salt, such as NaI, KI or n-Bu4NI (TBAI), rather than bromide or chloride salt, was found to play a key
role in the Pd(0)-catalyzed Heck reaction of aryl nonaflates and terminal alkenes. In the presence of
PdCl2(PPh3)2, NaI or TBAI in DMF, a class of 2-(1-alkenyl)phenylphosphonates was first synthesized via
the reaction of o-phosphonylphenyl nonaflates with alkenes, the yields, regioselectivities and
stereoselectivities were much dependent on the nature of the substituents. In case of the aryl
nonaflates without bearing the sterically hindered phosphonyl group with the alkenes, the reactions
proceeded more smoothly under the same conditions, leading to the linear products regioselectively in
good to excellent yields. A rationale for this reaction is discussed.
Received 24 May 2011
Received in revised form 18 June 2011
Accepted 22 June 2011
Available online 29 June 2011
Keywords:
Aryl nonaflates
Heck reaction
Phosphonates
Iodide additive
ß 2011 Elsevier B.V. All rights reserved.
1. Introduction
2. Results and discussion
In the last decades, aryl/vinyl nonaflates have attracted much
attention since in comparison of aryl/vinyl triflates, the nonaflates
are not only more stable and not prone to hydrolyze during
synthesis and handling, but display similar or slightly superior
reactivities in most of the metal-catalyzed cross-coupling reac-
tions and can be prepared easily from nonaflyl fluoride (NfF) which
We first examined the reaction of 4-chloro-2-phosphonylphe-
nyl nonaflate 1a with methyl acrylate 2a, and the results were
summarized in Table 1. Under standard Heck reaction conditions,
no desired reaction was detected (Entries 1–5, Table 1). After
conducting a series of examinations, we found that the presence of
iodide anion was essential for the success of this reaction. When
addition of 0.1 equiv. of anhydrous NaI, the starting material 1a
was consumed completely and the desired product 3a was isolated
in 80% yield with high regioselectivity and no other isomers were
observed (Entry 6, Table 1). Using NaI as a dihydrate (NaIÁ2H2O)
resulted in the same result, suggesting the presence of trace
amount of water has no unfavorable effect on the reaction (Entry 7,
Table 1). Other iodide salt, such as KI and n-Bu4NI (TBAI) were also
effective, while bromide salt or chloride salt, such as NaBr, NaCl,
LiCl, n-Bu4NCl (TBAC) could not make the reaction take place at all
(Entries 8–13, Table 1), indicating that iodide anion other than
chloride or bromide anion plays important role in this reaction.
Further reaction optimization demonstrated that DMF was the
best solvent and Et3N was the appropriate base.
To explore the scope and limitations of this reaction, the
reactions of 1a–c with several alkenes 2 (4 equiv.) were carried out
in the presence of PdCl2(PPh3)2 (0.05 equiv.), Et3N (4 equiv.), NaI
(0.1 equiv.) at 80–90 8C in DMF. As shown in Table 2, the yields,
regioselectivities and stereoselectivities were much dependent on
the nature of R1 and R2. As expected, the electron-deficient
nonaflate 1a (R1 = Cl) displayed good reactivity. The reaction of 1a
with activated methyl acrylate 2a proceeded smoothly, leading to
the trans linear product 3a absolutely (Entry 1, Table 2), while the
is
a commercially accessible, cheap, industrial product [1].
Generally, the addition of stoichiometric LiCl has benefical effects
in the coupling reactions of the nonaflates or triflates [2]. Recently,
we have demonstrated that 2-(1-alkynyl)phenylphosphonates
could be prepared conveniently via the reaction of the aryl
nonaflates with alkynes and the addition of excess LiCl indeed
improved the reactions [3]. However, during the course of our
investigation to synthesize the corresponding 2-(1-alkenyl)phe-
nylphosphonates via the Heck reaction of the same aryl nonaflates,
we found that the presence of iodide salt is necessary for the
reaction. Although the palladium-catalyzed Heck reaction is one of
the most well-established and valuable synthetic methods in
organic synthesis and has been investigated extensively [4], such
iodide anion effect and using aryl nonaflates with a hindered
ortho-phosphonyl group as substrates for the Heck reaction has
never been reported so far. Herein, we wish to report this
interesting iodide anion effect and its synthetic applications in this
paper.
* Corresponding author. Tel.: +86 020 84110918; fax: +86 020 84112245.
E-mail address: cespay@mail.sysu.edu.cn (A.-Y. Peng).
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.06.029

A.-Y. Peng et al. / Journal of Fluorine Chemistry 132 (2011) 982–986
983
Table 1
Optimization of the Heck reaction conditions of 1a and 2a.a
Entry
Solvent
Base (equiv.)
Additive (equiv.)
Temp. (time)
Yield 3a (%)
1
Dioxane
DMF
DMF
DMF
EtOH
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Cs2CO3 (1)
Et3N (4)
Et3N (4)
Et3N (4)
K2CO3 (2)
Et3N (4)
Et3N (4)
Et3N (4)
Et3N (4)
Et3N (4)
Et3N (4)
Et3N (4)
Et3N (4)
–
90 8C (8 h)
80 8C (8 h)
80 8C (8 h)
80 8C (8 h)
80 8C (8 h)
80 8C (6 h)
80 8C (6 h)
80 8C (6 h)
80 8C (6 h)
80 8C (6 h)
80 8C (6 h)
80 8C (6 h)
80 8C (6 h)
NRd
NR
NR
NR
NR
80e
83f
83f
83f
NR
NR
NR
NR
2
LiCl (3)
3
CuI (0.1)
LiCl (3)
4b
5c
6
DABCO (0.2)
NaI (0.1)
NaIÁ2H2O (0.1)
KI (0.1)
7
8
9
TBAI (0.1)
NaBr (0.1)
NaCl (0.1)
TBAC (0.1)
LiCl (0.1)
10
11
12
13
a
All reactions were catalyzed by 0.05 equiv. of PdCl2(PPh3)2 unless otherwise specified.
0.05 equiv. of Pd(OAc)2 and 0.1 equiv. of PPh3 were used as catalysts.
0.2 equiv. of CuI was used as catalyst.
b
c
d
e
f
NR means no reaction was detected by TLC and most starting material was recovered.
Isolated yield.
The yield was determined by 31P NMR spectral analysis of the crude reaction mixture.
Table 2
Iodide anion-mediated Heck reaction of 1 and 2.a
Entry
1 (R1)
2 (R2)
Additive (equiv.)
Yield (%)b
1
1a (Cl)
2a (COOMe)
2b (CN)
NaI (0.1)
NaI (0.1)
NaI (0.1)
NaI (0.1)
NaI (0.1)
TBAI (1)
NaI (0.1)
TBAI (1)
NaI (0.1)
TBAI (1)
NaI (0.1)
NaI (0.1)
TBAI (1)
3a (80)
3b (30)c
3c (65)d
3d (50)
Trace
2
1a (Cl)
3
1a (Cl)
2c (Ph)
4
1b (H)
2a (COOMe)
2b (CN)
5
1b (H)
6
1b (H)
2b (CN)
3e +4e (11)e
Trace
7
1b (H)
2c (Ph)
8
1b (H)
2c (Ph)
3f (60)d
Trace
3g + 4g (17)f
Trace
9
1c (MeO)
1c (MeO)
1c (MeO)
1c (MeO)
1c (MeO)
2a (COOMe)
2a (COOMe)
2b (CN)
10
11
12
13
2c (Ph)
Trace
3h + 5h (47)g
2c (Ph)
a
General reaction conditions: 1 (1 equiv.), 2 (4 equiv.), PdCl2(PPh3)2 (0.05 equiv.), Et3N (4 equiv.), NaI or TBAI in DMF at 80–90 8C for 6 h.
b
c
d
e
f
Isolated yield.
4b was isolated in about 28% yield but it was not very pure for full characterization (3b:4b is about 1:1 of the crude products from 31P NMR and 1H NMR).
Small amount of branched isomer 5 was detected by 31P NMR and 1H NMR.
3e:4e = 2:3 of the products from the 31P NMR and 1H NMR.
3g:4g = 4:1 of the products from the 31P NMR and 1H NMR.
g
3h:5h = 2.36:1 of the crude products from the 31P NMR and 1H NMR, accompany with an unidentified compound.

984
A.-Y. Peng et al. / Journal of Fluorine Chemistry 132 (2011) 982–986
Table 3
Iodide anion-mediated Heck reaction of 6 and 2.a
Entry
6 (R1)
2 (R2)
Additive (equiv.)
Yield (%)b
1
2
3
4
5
6
7
8
6a (Cl)
6a (Cl)
6a (Cl)
6a (Cl)
6b (H)
2a (COOMe)
2a (COOMe)
2a (COOMe)
2b (Ph)
LiCl (1)
–
7a (20)
7a (50)
7a (97)
7b (70)
7c (78)
7d (46)
Trace
NaI (0.1)
NaI (0.1)
NaI (0.1)
NaI (0.1)
NaI (0.1)
TBAI (1)
2a (COOMe)
2b (Ph)
6b (H)
6c (MeO)
6c (MeO)
2a (COOMe)
2a (COOMe)
7e (51)
a
General reaction conditions: 6 (1 equiv.), 2 (4 equiv.), PdCl2(PPh3)2 (0.05 equiv.), Et3N (4 equiv.), additive (0.1 equiv. or 1 equiv.) in DMF at 80–90 8C for 6 h.
Isolated yield.
b
reaction of 1a with acrylonitrile 2b gave a mixture of trans/cis
bearing phosphonyl group were then studied. As shown in Table 3,
the addition of 0.1 equiv. of NaI accelerated the reaction of 4-
chlorophenyl nonaflate 6a with methyl acrylate 2a significantly,
giving the desired product 7a in 97% yield entries (Entry 3, Table
3). However, the addition of 1 equiv. of LiCl did not promote but
retard this reaction (Entries 1 and 2, Table 3). This finding is
interesting since LiCl as additive has often shown stronger
promotion ability than the corresponding iodide salts in the cross
coupling reactions [2]. Similarly, under the same conditions,
compounds 6a and 6b reacted with the alkenes smoothly and
afforded the desired products 7b and 7d in good yields. The
reaction of the electron-rich 4-methoxyphenyl nonaflate 6c with
2a was also found to need the addition of 1 equiv. of TBAI, no
reaction was observed when using catalytic amount of NaI as
additive (Entries 7 and 8, Table 3).
The exact contribution of iodide anion in this reaction is still not
clear now. It is generally accepted that the halide additives
promote the cross-coupling reactions by accelerating the trans-
metallation step or by coordinating the halide to palladium prior to
oxidative addition [2,5]. One or more equiv. of chlorides or
bromides are usually used in the literature procedures. However,
in our present reaction, only catalytic amount of iodide additive is
needed in most cases and chloride or bromide salts are ineffective.
We reasoned that a Finkelstein replacement reaction [6] may occur
prior to the oxidative addition, in which aryl nonaflates
transformed to the more reactive aryl iodides (Scheme 1). That
is to say, the iodide anion would promote the reaction by
facilitating the exchange of nonaflate for iodide, which then can
enter the catalytic cycle of the Heck reaction. For the substrates
with electron-donating group (e.g. 1c and 6c), it is difficult to
proceed the Finkelstein replacement process, herein the iodide
additive seems not so effective.
isomers (3b:4b is about 1:1, Entry 2, Table 2). In the case of 1a with
styrene 2c, the reaction afforded the trans linear product 3c in 65%
yield with observation of branched isomer 5c formation (Entry 3,
Table 2). Further studies showed that the reactivity of 1b (R1 = H)
and 1c (R1 = OMe) decreased apparently. When using NaI as
additive, except that the reaction of 1b with 2a gave 3d in 50%
yield, other reactions of 1b and 1c with alkenes only led to
recovered starting materials and trace amount of the desired
products (Entries 5, 7, 9, 11, and 12, Table 2). To our delight, by
adding 1 equiv. of TBAI instead of 0.1 equiv. of NaI, all above
reactions took place at the end. For example, with the addition of
1 equiv. of TBAI, the reaction of 1b with 2b gave the product 3f in
60% isolated yield (Entry 8, Table 2). For this reaction, stoichio-
metric TBAI was necessary since most of the starting material was
recovered when the amount of TBAI was decreased to 0.5 equiv. In
this case, increasing the amount of NaI to 1 equiv. had no such
favourable effect. Unfortunately, even in the presence of 1 equiv. of
TBAI, the reactions of 1b with 2b and 1c with 2a or 2c only resulted
in mixtures of isomers in low yields, which were difficult to isolate
(Entries 6, 10, and 13, Table 2).
Regioselectivities and stereoselectivities were determined by
1H NMR spectral analysis of the crude reaction mixture. Generally,
the trans linear products 3 are the main products (Entries 1, 3, 4, 8,
10, and 13, Table 2). When using acryonitril as alkene substrate, the
reactions led to 1:1 or 2:3 mixtures of cis/trans-isomerized
products because of the small size of the nitril group (Entries 2
and 6, Table 2). In cases where styrene was used as alkene
substrate, branched products 5 were also observed other than the
main trans linear products (Entries 3, 8, and 13, Table 2).
To further examine the generality of such iodide anion effect on
the Heck reaction of aryl nonaflates, other aryl nonaflates without
3. Conclusions
The existence of a bulky phosphonyl group at the ortho position
of aryl nonaflates makes the nonaflates difficult to proceed the
Heck reaction under classical conditions. We found that
PdCl2(PPh3)2/iodide salt can facilitate the reaction, which is
efficient especially for electron-deficient aryl nonaflates. Iodide
salt additive was essential for the success of this Heck reaction,
while the corresponding chloride and bromide salts were
completely ineffective. We synthesized a series of 2-(1-alkenyl)-
phenylphosphonates for the first time using the present strategy,
these compounds have considerable potential as useful inter-
Scheme 1. Plausible mechanism of iodide anion-mediated Heck reaction of aryl
nonaflates.

A.-Y. Peng et al. / Journal of Fluorine Chemistry 132 (2011) 982–986
985
mediates for the following cyclization reactions. Further investiga-
tions on the scope of the reaction and the cyclization of 2-(1-
alkenyl)phenylphosphonates are underway.
4.2.3. [5-Chloro-2-((E)-styryl)-phenyl]-phosphonic acid diethyl ester
(3c)
Slightly yellow oil. IR (film): 2982, 1633, 1388, 1248, 1154,
1023 cmÀ1. 1H NMR (300 MHz, CDCl3):
d 7.96 (dd, J = 14.8, 2.7 Hz,
1H), 7.82 (d, J = 16.2 Hz, 1H), 7.68–7.74 (m, 1H), 7.47–7.56 (m, 3H),
7.28–7.39 (m, 3H), 7.03 (d, J = 16.2 Hz, 1H), 4.03–4.26 (m, 4H), 1.33
4. Experimental
(t, J = 7.0 Hz, 6H) ppm. 13C NMR (75 MHz, CDCl3):
d 139.30 (d, JC–
4.1. General
P = 9.2 Hz), 136.89, 133.98 (d, JC–P = 10.1 Hz), 133.00 (d, JC–
P = 19.5 Hz), 132.64, 131.97, 129.14, 128.81, 128.26 (d, JC–
P = 131.33 Hz), 128.25, 127.60, 126.89, 125.91 (d, JC–P = 4.2 Hz),
62.57 (d, JC–P = 4.4 Hz), 16.54 (d, JC–P = 6.2 Hz) ppm. 31P NMR
(121 MHz, CDCl3):
Calcd. for C18H20ClO3P (350.78): C, 61.63; H, 5.75. Found: C, 61.65;
H, 6.00.
The 1H, 13C and 31P NMR spectra were recorded on a Varian
Mercury-Plus 300 or Varian INOVA 400 NMR instrument. All
melting points are uncorrected. EI-mass spectra were recorded on
a Thermo DSQ EI-mass spectrometer. ESI-mass spectra were
recorded on a LCMS-2010A liquid chromatography mass spec-
trometer. HRMS were determined by a Thermo MAT95XP high
resolution mass spectrometer. IR spectra were recorded as KBr
pellets on a Bruker Equinox 55 FT/IR spectrometer. All commer-
cially available reagents were used as received. Column chroma-
tography was performed on 200–300 mesh silica gel. Thin-layer
chromatography was conducted on Kieselgel 60 F254. The starting
materials 1 and 6 were prepared according to our previous
procedures [3b].
d
17.84 ppm. MS (ESI): m/z: 351 [M+H]+. Anal.
4.2.4. (E)-3-[2-(diethoxy-phosphoryl)-phenyl]-acrylic acid methyl
ester (3d)
Slightly yellow oil. IR (film): 2985, 1719, 1637, 1392, 1247,
1024 cmÀ1 1H NMR (300 MHz, CDCl3):
. d 8.32 (d, J = 15.9 Hz, 1H),
7.97–8.05 (m, 1H), 7.65–7.70 (m, 1H), 7.52–7.58 (m, 1H), 7.41–7.48
(m, 1H), 6.36 (d, J = 15.9 Hz, 1H), 4.03–4.26 (m, 4H), 3.81 (s, 3H),
1.33 (t, J = 7.0 Hz, 6H) ppm. 13C NMR (75 MHz, CDCl3):
d 166.81,
143.19 (d, JC–P = 4.4 Hz), 137.79 (d, JC–P = 6.5 Hz), 134.44 (d, JC–
P = 9.8 Hz), 132.71, 129.35, 128.00 (d, JC–P = 172.3 Hz), 127.19 (d,
JC–P = 13.5 Hz), 120.81, 62.54 (d, JC–P = 5.2 Hz), 51.95, 16.49 (d, JC–
4.2. Typical procedure for iodide anion-mediated Heck reaction of 1
and 2 or 6 and 2
P = 6.5 Hz) ppm. 31P NMR (121 MHz, CDCl3):
d 18.40 ppm. MS (ESI):
To a mixture of 1 (0.5 mmol), PdCl2(PPh3)2 (0.025 mmol), Et3N
(2.0 mmol), NaI (0.050 mmol) or n-Bu4NI (0.5 mmol), and DMF
(3.0 mL) was added dropwise the terminal alkene 2 (2.0 mmol) at
room temperature. After stirring at 80–90 8C for 6 h under
nitrogen, the reaction mixture was diluted with EtOAc and washed
with aqueous NH4Cl until neutral and brine, dried (Na2SO4), and
evaporated in vacuo. The residue was chromatographed on silica
gel using hexane/EtOAc (6:1–4:1) as eluent to give the correspond-
ing products. Among these products, compounds 3, 4 and 5 are new
compounds; compounds 7a–e are known compounds which were
confirmed by the results of NMR spectra and MS (ESI) data
compared to the literature values.
m/z: 299 [M+H]+. Anal. Calcd. for C16H24ClO3P (330.79): C, 56.37; H,
6.42. Found: C, 56.52; H, 6.63.
4.2.5. Mixture of [2-((E)-2-cyano-vinyl)-phenyl]-phosphonic acid
diethyl ester (3e) and [2-((Z)-2-cyano-vinyl)-phenyl]-phosphonic acid
diethyl ester (4e)
Slightly yellow oil. IR (film): 2922, 2219, 1627, 1246, 1147,
1023 cmÀ1. 1H NMR (300 MHz, CDCl3):
d 8.18 (d, J = 16.2 Hz, 0.4H),
7.96–8.07 (m, 2H), 7.49–7.65 (m, 2.6H), 5.86 (d, J = 16.2 Hz, 0.4H),
5.61 (d, J = 12.0 Hz, 0.6H), 4.01–4.27 (m, 4H), 1.31–1.38 (m,
6H) ppm. 13C NMR (75 MHz, CDCl3):
d 149.19, 148.47, 136.63 (d, JC–
P = 9.2 Hz), 134.63, 134.21, 132.91, 130.30, 130.10, 129.95, 129.76,
128.95, 126.80, 126.57, 126.41, 117.16, 116.79, 99.26, 98.48, 62.65
4.2.1. (E)-3-[4-chloro-2-(diethoxy-phosphoryl)-phenyl]-acrylic acid
methyl ester (3a)
(d, JC–P = 4.6 Hz), 16.53 (br s) ppm. 31P NMR (121 MHz, CDCl3):
d
17.79, 17.77 ppm. MS (EI): m/z (%) = 265 (26) [M+], 237 (23), 220
White solid. Mp: 62–64 8C. IR (KBr): 2986, 1725, 1637, 1248,
(35), 208 (34), 182 (100), 156 (44), 128 (14). HRMS (EI) calcd. for
C
13H15ClNO3P (M+): 265.0862. Found: 265.0861.
1164, 1023 cmÀ1. 1H NMR (300 MHz, CDCl3):
d
8.31 (d, J = 15.8 Hz,
1H), 8.01 (dd, J = 15.0, 2.3 Hz, 1H), 7.60–7.65 (m, 1H), 7.49–7.54 (m,
1H), 6.35 (d, J = 15.8 Hz, 1H), 4.05–4.29 (m, 4H), 3.83 (s, 3H), 1.35 (t,
4.2.6. [2-((E)-styryl)-phenyl]-phosphonic acid diethyl ester (3f)
Colorless oil. IR (film): 2982, 1634, 1392, 1245, 1138,
1025 cmÀ1 1H NMR (300 MHz, CDCl3):
. d 7.93–8.01 (m, 1H),
7.88 (d, J = 16.2 Hz, 1H), 7.74–7.87 (m, 1H), 7.48–7.55 (m, 3H),
7.23–7.38 (m, 4H), 7.04 (d, J = 16.2 Hz, 1H), 4.00–4.26 (m, 4H), 1.30
(td, J = 7.0, 0.3 Hz, 6H) ppm. 13C NMR (75 MHz, CDCl3):
d 140.88 (d,
J = 7.1 Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3):
d
166.79, 142.06
(d, JC–P = 4.2 Hz), 136.18 (d, JC–P = 7.9 Hz), 135.75, 134.43 (d, JC–
P = 10.4 Hz), 132.86 (d, JC–P = 2.3 Hz), 130.28 (d, JC–P = 181.9 Hz),
128.68 (d, JC–P = 14.6 Hz), 121.27, 62.87 (d, JC–P = 5.7 Hz), 52.03,
16.41 (d, JC–P = 6.1 Hz) ppm. 31P NMR (121 MHz, CDCl3):
d
16.32 ppm. MS (ESI): m/z: 333 [M+H]+. Anal. Calcd. for C14H18ClO5P
JC–P = 9.4 Hz), 137.14, 134.28 (d, JC–P = 9.2 Hz), 132.60, 131.40,
130.86, 128.70, 127.95, 127.05 (d, JC–P = 5.8 Hz), 126.80, 126.04 (d,
JC–P = 13.8 Hz), 124.69, 62.18 (d, JC–P = 4.1 Hz), 16.50 ppm. 31P NMR
(332.72): C, 50.54; H, 5.45. Found: C, 50.71; H, 5.59.
4.2.2. [5-Chloro-2-((E)-2-cyano-vinyl)-phenyl]-phosphonic acid
diethyl ester (3b)
(121 MHz, CDCl3): d
20.06 ppm. MS (ESI): m/z: 317 [M+H]+, 339
[M+Na]+. Anal. Calcd. for C18H21O3P (316.33): C, 68.34; H, 6.69.
Found: C, 68.19. H, 6.61.
White solid. Mp: 83–85 8C. IR (KBr): 2922, 2217, 1622, 1246,
1155, 1028 cmÀ1. 1H NMR (300 MHz, CDCl3):
d
8.02 (d, J = 16.5 Hz,
1H), 7.90 (dd, J = 15.0, 2.0 Hz, 1H), 7.44–7.54 (m, 2H), 5.82 (d,
J = 16.5 Hz, 1H), 3.97–4.20 (m, 4H), 1.28 (t, J = 7.1 Hz, 6H) ppm. 13
NMR (75 MHz, CDCl3): 147.87 (d, JC–P = 3.4 Hz), 136.77 (d, JC–
4.2.7. Mixture of (E)-3-[2-(diethoxy-phosphoryl)-4-methoxy-
phenyl]-acrylic acid methyl ester (3g) and (Z)-3-[2-(diethoxy-
phosphoryl)-4-methoxy-phenyl]-acrylic acid methyl ester (4g)
Slightly yellow oil. IR (film): 2983, 1718, 1636, 1245, 1175,
1025 cmÀ1. 1H NMR (300 MHz, CDCl3):
d 8.26 (d, J = 15.8 Hz, 0.8H),
7.40–7.64 (m, 2.2H), 6.93–7.03 (m, 1H), 6.23 (d, J = 15.8 Hz, 0.8H),
5.94 (d, J = 12.9 Hz, 0.2H), 3.92–4.24 (m, 4H), 3.81 (s, 2.4H), 3.80 (s,
0.6H), 3.74 (s, 2.4H), 3.58 (s, 0.6H), 1.21–1.32 (m, 6H) ppm. 13C
C
d
P = 19.8 Hz), 134.84 (d, JC–P = 8.2 Hz), 134.36 (d, JC–P = 9.8 Hz),
132.87, 130.09 (d, JC–P = 181.4 Hz), 127.84 (d, JC–P = 14.6 Hz),
117.45, 99.68, 63.10 (d, JC–P = 5.7 Hz), 16.53 (d, JC–P = 5.9 Hz) ppm.
31P NMR (121 MHz, CDCl3):
d 15.66 ppm. MS (ESI): m/z: 300
[M+H]+, 322 [M+Na]+. Anal. Calcd. for C13H15ClNO3P (299.69): C,
52.10; H, 5.04; N, 4.67. Found: C, 51.94; H, 5.24; N, 4.43.
NMR (75 MHz, CDCl3):
d 166.97, 166.16, 160.07 (d, JC–P = 18.2 Hz),

986
A.-Y. Peng et al. / Journal of Fluorine Chemistry 132 (2011) 982–986
159.01 (d, JC–P = 18.1 Hz), 142.92, 142.47, 132.17, 131.95, 130.75,
129.63 (d, JC–P = 8.1 Hz), 128.74 (d, JC–P = 5.7 Hz), 128.46 (d, JC–
P = 16.5 Hz), 119.62, 119.01 (d, JC–P = 10.6 Hz), 118.70, 118.47 (d,
JC–P = 13.5 Hz), 118.25 (d, JC–P = 6.6 Hz), 117.36 (d, JC–P = 8.4 Hz),
62.45 (d, JC–P = 4.1 Hz), 62.21 (d, JC–P = 4.0 Hz), 55.64, 55.49, 51.67,
Acknowledgments
This work was supported by the research grants from the
National Natural Science Foundation of China (Grant No. 20602043)
and the Fundamental Research Funds for the Central Universities.
51.22, 16.36 (br s) ppm. 31P NMR (121 MHz, CDCl3):
d 18.51,
18.26 ppm. MS (EI): m/z (%) = 328 (21) [M+], 269 (84), 241 (35), 213
(100), 191 (56), 149 (53). HRMS (EI) calcd. for C15H21O6P (M+):
328.1070. Found: 328.1069.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jfluchem.2011.06.029.
4.2.8. (E)-3-(4-chloro-phenyl)-acrylic acid methyl ester (7a) [7]
White solid. Mp: 73–76 8C.1H NMR (300 MHz, CDCl3):
d
7.59 (d,
J = 15.9 Hz, 1H), 7.31–7.39 (m, 4H), 6.36 (d, J = 15.9 Hz, 1H), 3.77 (s,
3H) ppm. 13C NMR (75 MHz, CDCl3):
167.01, 143.30, 136.13,
References
d
[1] (a) Q. Chen, Z. Yang, Tetrahedron Lett. 27 (1986) 1171–1174;
(b) F. Aulenta, H.U. Reissig, Synlett (2006) 2993–2996;
1332.80, 129.17, 129.11, 118.34, 51.86 ppm. MS (ESI): m/z: 197
[M+H]+.
(c) Q. Chen, Y. He, Chin. J. Chem. 5 (1990) 451–468;
(d) F. Aulenta, M. Berndt, I. Brudgam, H. Hartl, S. Sorgel, H.U. Reissig, Chem. Eur. J.
13 (2007) 6047–6062;
(e) V.V. Rostovtsev, L.M. Bryman, C.P. Junk, M.A. Harmer, L.G. Carcani, J. Org. Chem.
73 (2008) 711–714;
4.2.9. 1-Chloro-4-((E)-styryl)-benzene (7b) [8]
White solid. Mp: 124–125 8C. 1H NMR (300 MHz, CDCl3):
d
7.25–7.53 (m, 9H), 7.07 (d, J = 1.6 Hz, 2H) ppm. 13C NMR (75 MHz,
CDCl3): 137.00, 135.87, 133.19, 129.35, 128.87, 128.77, 127.90,
(f) D. Xu, Z.H. Liu, W.J. Tang, J. Mo, L.J. Xu, Chin. Chem. Lett. 19 (2008) 1017–1020;
(g) J. Hogermeier, H.U. Reissig, Adv. Synth. Catal. 351 (2009) 2747–2763.
[2] (a) E.K. Yum, S.K. Kang, J.K. Choi, Bull. Korean Chem. Soc. 22 (2001) 644–646;
(b) A.L. Casado, P. Espinet, A.M. Gallego, J. Am. Chem. Soc. 122 (2000) 11771–
11782;
d
127.69, 127.40, 126.58 ppm. MS (ESI): m/z: 215 [M+H]+.
4.2.10. (E)-3-phenyl-acrylic acid methyl ester (7c) [7]
(c) A.H. Roy, J.F. Hartwig, Organometallics 23 (2004) 194–202;
(d) M. Fujita, H. Oka, K. Ogura, Tetrahedron Lett. 36 (1995) 5247–5250;
(e) C.A. Merlic, M.F. Semmelhack, J. Organomet. Chem. 391 (1990) C23–C27;
(f) K. Fagnou, M. Lautens, Angew. Chem. Int. Ed. 41 (2002) 26–47.
[3] (a) A. Peng, B. Li, X. Yang, J. Lin, Synthesis (2008) 2412–2416;
(b) A. Peng, X. Zhang, Y. Ding, Heteroat. Chem. (2005) 529–534.
[4] (a) I.P. Beletskaya, A.V. Cheprakov, Chem. Rev. 100 (2000) 3009–3066;
(b) A.B. Dounay, L.E. Overman, Chem. Rev. 103 (2003) 2945–2963;
(c) M. Larhed, A. Hallberg, in: E.-i. Negishi, A.d. Meijere (Eds.), Handbook of
Organopalladium Chemistry for Organic Synthesis, Wiley-Interscience, New York,
2002, p. 1133;
Slightly yellow oil. 1H NMR (300 MHz, CDCl3):
d
7.70 (d,
J = 16.0 Hz, 1H), 7.51–7.54 (m, 2H), 7.36–7.39 (m, 3H), 6.45 (d,
J = 16.0 Hz, 1H), 3.82 (s, 3H) ppm. 13C NMR (75 MHz, CDCl3):
167.36, 144.85, 134.36, 130.29, 128.89, 128.07, 117.80, 51.83 ppm.
MS (ESI): m/z: 163 [M+H]+, 185 [M+Na]+, 201 [M+K]+.
d
4.2.11. (E)-Stilbene (7d) [6,9]
White solid. Mp: 130–132 8C.1H NMR (300 MHz, CDCl3):
d
7.52–
7.56 (m, 4H), 7.35–7.41 (m, 4H), 7.27–7.31 (m, 2H), 7.13 (s,
2H) ppm. 13C NMR (75 MHz, CDCl3):
137.35, 128.72, 127.65,
126.55 ppm. MS (ESI): m/z: 181 [M+H]+.
(d) V. Coeffard, P.J. Guiry, Curr. Org. Chem. 14 (2010) 212–229;
(e) C. Amatore, A. Jutand, Acc. Chem. Res. 33 (2000) 314–321;
(f) W. Cabri, I. Candiani, Acc. Chem. Res. 28 (1995) 2–7.
d
[5] G.T. Achonduh, N. Hadei, C. Valente, S. Avola, C.J. O’Brien, M.G. Organ, Chem.
Commun. 46 (2010) 4109–4111.
[6] (a) J. Limanto, A. Shafiee, P.N. Devine, V. Upadhyay, R.A. Desmond, B.R. Foster, D.R.
Gauthier, R.A. Reamer, R.P. Volante, J. Org. Chem. 70 (2005) 2372–2375;
(b) M. Hanack, J. Ullmann, J. Org. Chem. 54 (1989) 1432–1435.
[7] Z.H. Zhang, Z.G. Zha, C.S. Gan, C.F. Pan, Y.Q. Zhou, Z.Y. Wang, M.M. Zhou, J. Org.
Chem. 71 (2006) 4339–4342.
[8] W. Prukala, M. Majchrzak, C. Pietraszuk, B. Marciniec, J. Mol. Catal. A: Chem. 254
(2006) 58–63.
[9] M. Mahesh, J.A. Murphy, H.P. Wessel, J. Org. Chem. 70 (2005) 4118–4123.
4.2.12. (E)-3-(4-methoxy-phenyl)-acrylic acid methyl ester (7e) [7]
White solid. Mp: 89–93 8C.1H NMR (300 MHz, CDCl3):
7.65 (d,
J = 16.0 Hz, 1H), 7.45–7.49 (m, 2H), 6.88–6.92 (m, 2H), 6.31 (d,
J = 15.9 Hz, 1H), 3.84 (s, 3H), 3.80 (s, 3H) ppm. 13C NMR (75 MHz,
d
CDCl3):
d 167.71, 161.35, 144.52, 129.74, 127.15, 115.30, 114.35,
55.53, 51.74 ppm. MS (ESI): m/z: 193 [M+H]+.