An efficient palladium catalyzed Mizoroki-Heck cross-coupling in water

Article abstract of DOI:10.1039/c7gc02869e

The homogeneous Pd-catalysed Mizoroki-Heck coupling reaction was successfully performed in water in the absence of any additives under aerobic conditions. The various key reaction parameters that affect the yield of the desired cross-coupling product were optimized. The Pd(PPh₃)₄/Et₃N/H₂O/98 °C catalyst system was found to be highly active (TOF = 12 to 14 h^-1) towards achieving excellent yield of the Mizoroki-Heck coupling products for a wide range of electron-withdrawing as well as electron-donating aryl bromides and chlorides in the shortest reaction time. Pd(PPh₃)₄ catalyst deactivation during the Mizoroki-Heck coupling reaction was investigated and to evolve a strategy for achieving ten times Pd-metal recyclability without appreciable loss of its activity. Thus, the proposed mechanism provides access to a variety of olefins in aqueous medium, making this protocol eco-friendly.

Full text of DOI:10.1039/c7gc02869e

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DOI: 10.1039/C7GC02869E
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ARTICLE
An Efficient Palladium Catalyzed Mizoroki-Heck Cross-
Coupling in Water
Received 00th January 20xx,
Accepted 00th January 20xx
Sanjay N. Jadhav, Chandrashekhar V. Rode*
DOI: 10.1039/x0xx00000x
The homogeneous Pd-catalysed Mizoroki-Heck coupling reaction has been successfully conducted in water in
the absence of any additives under aerobic condition. The various key reaction parameters that affect the yield
of desired cross coupling product were optimized. Pd(PPh3)4/Et3N/H2O/98 °C catalyst system was found to be
highly active (TOF= 12 to14 h-1) towards achieving the excellent yield of the Mizoroki-Heck coupling
products for a wide range of electron withdrawing as well as electron donating aryl bromide and chlorides in
shortest reaction time. The Pd(PPh3)4 catalyst deactivation during Mizoroki-Heck coupling reaction has been
identified, which evolved a strategy for Pd-metal recyclability over ten times without appreciable loss of its
activity. Thus, it provides access to variety of olefins in aqueous medium, making this protocol eco-friendly.
www.rsc.org/
Introduction
cross coupling reaction has been attempted recently.8 Although
In the 21st century, an organic chemist faces intimidating
challenges to design a ‘green’ protocol which is able to make the
organic transformations sustainable and economically beneficial.1
Among various challenges, the use of greener reaction solvent is
one of the most important constituents in any chemical processes.
The reaction solvent is a key driver in deciding toxicity, hazards,
cost, and waste generation of a particular process.2 Water a
‘nature’s choice of solvent’ having several unique characteristic
for organic synthesis is very attractive from both economic and
environmental perspectives. It is a sustainable alternative because
of its comparatively high vapour pressure with respect to organic
solvents. Importantly, ‘water’ is the primary and the only solvent
in various chemical reactions of life. These properties of the
water encourage researchers to explore the use water as a solvent
for the chemical processes in various challenging reactions such
as, Pd catalysed C-C cross coupling reactions.3
the Mizoroki-Heck reaction was strongly benefited from aqueous
chemistry, water has not been considered to be an appropriate
solvent for the synthesis because most of the chloro or bromo
aryl halides are insoluble in water, making the reaction mixture
heterogeneous and thereby retarding rate of reaction with low
yield of the desired product. To overcome such drawbacks,
alternate attempts like designing water-soluble ligands,9 using
inorganic salt promoters,10 adding phase-transfer agents,11 using
alternative energy sources like microwave or ultrasound,12 and
co-solvents were reported.13
Considering the importance of water as an environmentally
benign reaction media for Pd catalysed reactions14 we report
here, Pd(PPh3)4/Et3N/H2O as a simple and efficient catalyst
system for coupling of aryl bromides and chlorides with olefins
as well as trimethylsillyl acrylate without any additive.
The transition metals, especially Pd-catalysts have revolutionized
the art and practice of organic synthesis for the construction of
various pharmaceuticals, agrochemical and compounds of
theoretical interests by carbon-carbon and carbon-heteroatom
bonds.4 Among several different protocols that have been
reported till date, special interest has been devoted to the
Mizoroki-Heck cross-couplings of aryl and vinyl halides with
terminal olefins for the facile synthesis of cinammates and
stilbene.5 This coupling reaction has been extensively studied and
widely used in both academia and industry due to the mild
conditions applied to activation of olefins.7 The Mizoroki-Heck
reaction if carried out in water under ambient conditions, would
bring the radical improvement in the development of chemical
industrial processes.7
Results and Discussion
Initially, screening of several organic and inorganic bases for the
Mizoroki-Heck cross coupling reaction of 4-bromoanisole with t-
butyl acrylate using Pd(PPh3)4 (2 mol %) was carried out in water
at reflux condition, and the results are summarized in Table 1. It
was observed that water soluble inorganic bases such as K3PO4,
NaOH and K2CO3 showed poor activity (Table 1, entries 1-3).
Then, a series of organic bases were tested for the same protocol
(Table 1, entries 4-15) among which triethylamine was the most
efficient base that gave 90% yield of the desired product in 3h
(Table 1, entry 4). Interestingly, under the same reaction
conditions, sterically hindered tripropylamine and tributyl amines
gave product yield of only 45 and 20%, respectively (Table 1,
entries 6 and 7). Cyclic amines such as morpholine, DBU and
DABCO were also examined (Table 1, entries 10, 11, 15) and
The use of neat water in palladium catalysed Mizoroki-Heck
only morpholene gave
a moderate yield (38 %). Thus
triethylamine showing the highest efficiency plays a dual role. It
acts as a base15 as well as a ligand in Heck reaction16 because, it
has much higher tendency to coordinate Pd to form the active Pd-
Chemical Engineering and Process Development Division, CSIR-National
Chemical Laboratory, Pune 411008, M. S. India.
Electronic Supplementary Information (ESI) available: 1H and 13C NMR spectrum for
all the synthesized products see DOI: 10.1039/x0xx00000x
complex. As
a
consequence, also triethylamine forming
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ammonium salts which is able to stabilize Pd-active species in
water.16c
used, as expected the product yields increased significantly
DOI: 10.1039/C7GC02869E
(Table 2, entries 3 and 8). In this comparative investigation, if a
View Article Online
Table 1. The effect of base on the cross-coupling of 4-
heterogeneous catalyst like Pd/C was used, even after long
reaction time of 12h (TOF=8 h-1), the product yield (Table 2,
entry 4) was much less than that of Pd(PPh3)4 within the 3 h
(TOF=12 h-1). In order to evaluate the effect of catalyst loading,
model reaction was carried out using different concentrations of
Pd(PPh3)4. It was observed that among different loadings, 2 mol
% Pd(PPh3)4 offered quantitative yields (90%) of product in a
shortest time of 3 h at 98 C (Table 2, entry 8). No significant
improvement was observed by using increased amount of 3 mol
% catalyst (Table 2, entry 10).
The presence of O2 in the reaction media played a crucial role in
the catalytic activity. To investigate the influence of the O2
present in air, we performed the model reaction under air, O2 and
N2 atmosphere and results are illustrated in Figure 1. When the
Heck reaction was carried out under N2 atmosphere catalytic
efficiency of catalytic system was comparatively less as
compared to the reactions carried out in air and O2. The kinetic
study clearly indicated that the higher yields were obtained under
air and O2, than those obtained under N2 atmosphere in the same
reaction time. This was due to the continuous reoxidation of
Pd(0) species under air or O2 preventing agglomeration of Pd+2 to
inactive Pd0 black.16, 17 When the model reaction was performed
with I2 as a re-oxidant under N2 (Fig.1), the re-activation of the
palladium black with I2 was also successful giving the same
performance as compared with the reaction performed under air
or O2. This fact clearly indicates that the oxygen helps re-
oxidation of Pd atoms on the surface.17b
bromoanisole with t-butyl acrylatea
Br
COOt-Bu
98 oC
Pd(PPh3)4
COOt-Bu
+
Base, H2O
MeO
MeO
Entry
Base
Time (h)
Yieldb (%)
1
2
3
K3PO4
NaOH
K2CO3
Et3N
12
12
12
3
30
40
70
4
90
5
6
7
8
(i-Pr)2NH
(n-Pr)2NH
(n-Bu)3N
n-PrNH2
i-PrNH2
DABCO
DBU
Me2NH
12
12
12
12
12
12
12
12
12
12
12
40
45
20
14
Trace
10
Trace
Trace
Trace
Trace
38
9
10
11
12
13
14
15
Pipyridine
Pyrrolidine
Morpholine
aReaction conditions: 4-bromoanisole (1 mmol), t-butyl acrylate
(1 mmol), Pd(PPh3)4 (2 mol %), bases (2 mmol), H2O (5 mL), 98
C, air, 3h. bIsolated yields after column chromatography.
Table 2. The effect of catalyst precursors on cross-
coupling of 4-bromoanisole with t-butyl acrylatea.
To investigate the effect of temperature on the catalytic system,
the model reaction was carried out at different temperatures (40-
98 C) and the results are shown in Figure 2. When the
temperature was increased from 40 to 80 C, the product yield
increased substantially from 8 to 65%, but a very significant
enhancement to 90% was observed for a rise in temperature in
the range of 90-98C.
COOt-Bu
Br
98 oC
Pd-species,
COOt-Bu
+
Et3N, H2O
MeO
MeO
Yieldb
Conversion
Entry
[Pd]
Mol
(%)
2
2
2
2
2
2
2
2
2.5
3
1.5
1
Time
(h)
12
12
12
12
12
12
12
3
(%)
(%)
56
60
67
63
69
73
80
90
90
91
80
60
1
2
3
4
5
6
7
8
9
Pd(OAc)2
PdCl2
Pd2(dba)3
Pd/C (10 %)
PdCl2(CH3CN)2
PdCl2(PPh3)2
Pd(dppf)Cl2
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
60
61
70
70
73
82
86
97
98
97
89
66
3
3
3
3
10
11
12
aReaction conditions: 4-bromoanisole (1 mmol), t-butyl acrylate (1
mmol), Pd precursors (mol %), Et3N (2 mmol), H2O (5 mL), 98 C,
air, 3h. bIsolated yields after column chromatography.
The efficiency of various palladium precursors was also
examined in the model reaction of coupling (Table 2). The results
indicated that all the precursors containing Pd(II) species
exhibited moderate catalytic activity both in the absence and in
the presence of a ligand (Table 2, entries 1, 2, and 5-7). However,
zerovalent Pd sources such as Pd2(dba)3 and Pd(PPh3)4 when
Figure 1. Yield vs. Time curves of the reactions of 4-
bromoanisole with t-butyl acrylate under air, O2, N2 and I2 in N2
atmosphere .
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hindered acrylates to achieve high yields as compaVrieedw Awrtiicthle Ootnhlineer
DOI: 10.1039/C7GC02869E
simple acrylates under the same reaction conditions. As sulphur
containing compounds are the most common units in
pharmaceutically active compounds, we further investigated the
Mizoroki-Heck reaction of 3-bromothiophene with acrylates. It
was observed that the present catalytic system was applicable for
the cross-coupling of 3-bromothiophene and acrylates with 88 to
93 % yield in 3 h (Table 4, entries 21-24). It was found that the
present protocol was efficient to achieve good to excellent yields
of cinnamate derivatives in 3h. From the 1H NMR spectrums
confirmed the E- and Z-isomers from the J coupling values. It
was observed that the ratio of E/Z isomers was dramatically
affected by the nature of the substituent present on the aryl
halides. The compounds containing electron withdrawing and
donating groups showed 100% E-isomers. 1-Naphthyl bromide
reacted with different acrylates to give a 50:50 mixture of (E/Z)
isomer ratio (Table 4, entries 33-36) due to the steric hindrance
of 1-Naphthyl bromide. The excellent tolerance of the catalyst
system to various functional groups was evident in terms of TOF
values which were in the range of 12 to 14 h-1.
Figure 2. Temperature effects on the reaction of 4-bromoanisole
with t-butyl acrylate at different temperatures.
Reaction conditions: 4-bromoanisole (1 mmol), t-butyl acrylate
(1 mmol), Pd(PPh3)4 (2 mol %), Et3N (2 mmol), H2O (5 mL),
40-98 C, air, 3h. GC yields.
These excellent results obtained with aryl bromides, encouraged
us to employing the developed protocol for several aryl chlorides
with various acrylates. From a practical point of view, the
utilization of the easily available and inexpensive aryl chlorides
is highly desirable.19 The activation of the aryl chlorides is much
more difficult than aryliodides and bromides.20
Figure 3 shows the effect of the reaction time on the yield of the
final product. The model reaction carried out in a time range of
20 to 200 minutes. The percentage yield of the final product line
linearly increased with the increase in the reaction time from 20
to 180 min and after that it remained constant giving 90 % yield.
The effect of concentration of substrate in moles/L was also
studied. When the concentration of 4-bromoanisole decreased,
the product yield increased from 73% to 90% (Table 3, entries 1-
4). Very interestingly, if the substrate concentration was
decreased further, the product yield again dropped down to 69 %
(Table 3, entries 5-6). These results revealed that the ratio of
moles of 4-bromoanisole to solvent (water in liters) plays
important role in present catalytic system.
Therefore, one of the challenges in developing of high-
performance catalytic protocol for the coupling of inactive aryl
chlorides and acrylates is of great interest. The efficiency of the
present catalytic protocol was found to be moderate for the
variety of aryl chlorides as demonstrated by the results in Table
5. Various 4-substituted aryl chlorides containing either electron-
The results for effect of concentration of aryl bromide on the
Pd(PPh3)4 catalyzed Mizoroki-Heck reaction of 4-bromoanisol
and t-butyl acrylate was indicated in Fig. 4. As the mmols of 4-
bromoanisol increases from 1 to 1.5 the initially yield increases
steadily and showed 90 % yield in the same period of time. It is
interesting to note that, when the amount of 4-bromoanisol was
increased from 2.0 to 3.0 mmols, the resulting yield of the
desired product dropped from 90 % to 80 % in 3h. By adding an
additional mmols of 4-bromoanisol, the detrimental effect on the
yield of desired product, which clearly indicates the excess use of
4-bromoanisol is not attractive for present protocol.
The scope and generality of the optimized protocol was explored
for Mizoroki-Heck arylation of a variety of aryl bromides and
olefins.The reactions were conducted with 2 mol % of Pd(PPh3)4
catalyst and 2.0 mmol of Et3N at 98 °C in water for 3 h, and the
results are presented in Table 4. It was observed that various 4-
substituted aryl bromides bearing both electron withdrawing and
electron donating groups with different olefins such as –NO2, -
Me, -Cl, -OMe, -F, Ph, PhCO- and -COCH3 afforded the desired
arylation products in good to excellent yields.This catalytic
system could tolerate aryl halides with bulky and sterically
Figure 3. The effect of reaction time on the yield of the desired
product.
Reaction conditions: 4-bromoanisole (1 mmol), t-butyl acrylate
(1 mmol), Pd(PPh3)4 (2 mol %), Et3N (2 mmol), H2O (5 mL), 98
C, air, 20-200 min. GC yields.
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Mizoroki-Heck reaction, we studied the reactionVibewetAwrteicelenOanlrinyel
DOI: 10.1039/C7GC02869E
bromide with allyltrimethylsilane (Scheme 1). It was observed
that the reaction proceeded with moderate to good yield in 3h
1
with E/Z isomers. As per the J coupling values of the H NMR
spectrum it was found that desired product having 50:50 mixture
of the E-and Z-isomers. Further detailed study is in progress in
our laboratory to investigate the various reaction parameters such
as selectivity and substrate scope of various aryl bromides and
chlorides with allyltrimethylsilane in aqueous medium.
Br
Si
Pd(PPh3)4
Et3N, H2O
Si
+
98 o
C
79 %, E:Z= 50:50
Scheme 1. Regioselective Mizoroki-Heck reaction of
allyltrimethylsilane with aryl bromide in water.
Figure 4. The effect of concentration of aryl bromides on the
Pd(PPh3)4 catalyzed Mizoroki-Heck reaction of 4-bromoanisol
and t-butyl acrylate.
Reaction conditions: 4-bromoanisole (1-3 mmol), t-butyl
acrylate (1 mmol), Pd(PPh3)4 (2 mol %), Et3N (2 mmol), H2O (5
mL), 98 C, air, 3h. GC yields.
Catalyst Reusability Study
As it was a homogeneous Pd(PPh3)4 catalyst, it could be retained
in the reaction flask after extracting the desired product by (ethyl
acetate 3X10 mL) in the first run and the reaction was continued
by charging new substrates to the flask containing the used
catalyst. However, the catalyst did not show the activity after 3h.
The catalyst stability was studied with the help of 31P-NMR (Fig.
5). 31P-NMR of the fresh Pd(PPh3)4 catalyst, the phosphorus
chemical shift was at 23.3 ppm.
donating 4-methoxy-chlorobenzene or electron-withdrawing 4-
nitro-chlorobenzene groups gave the analogous products in
moderate yields in 12 h (Table 5, entries 1–8). Sterically hindered
t-butyl acrylate and butyl acrylate were also successfully coupled
with 4-nitro-chlorobenzene and 4-methoxy-chlorobenzene giving
moderate yield in 12h at 98 C (Table 5, entries 1, 2, 5, 6).
Table 3. Effect of substrate concentration in Mizoroki-
Heck coupling of t-butyl acrylate and 4-bromoanisole a.
COOt-Bu
Br
Pd(PPh3)4, 98 oC
COOt-Bu
+
Et3N, H2O
MeO
MeO
Entry
4-Bromoanisole
(mmol)
4-Bromoanisole/H2O
mol/L
Yieldb
(%)
Figure 5. 31P-NMR spectra for the (A) TPP ligand, (B) fresh
Pd(PPh3)4 catalyst (C) O=PPh3 and (D) recovered catalyst.
1
2
3
4
5
6
40
30
20
10
5
0.4
0.3
0.2
0.1
0.05
0.01
73
85
90
90
81
69
For the recovered catalyst, there was only one peak observed at
29.30 ppm corresponding to O=PPh3, which clearly matched with
the standard 31P spectrum of the O=PPh3 while the initial peak
totally disappeared. The results confirmed the dissociation of the
PPh3 ligand from the precursor leading to the oxidation of the
ligand to O=PPh3. The dissociated Pd was deactivated due to the
agglomerization which was evident by the presence of black
particles in the reaction crude.
1
aReaction conditions: 4-bromoanisole (1 mmol), t-butyl acrylate (1
mmol), Pd(PPh3)4 (2 mol %), Et3N (2 mmol), H2O (100 mL), 98 C,
air, 3h. bIsolated yields after column chromatography.
In addition, the scope of regioselective Mizoroki-Heck reaction
was explored for the arylation of allyltrimethylsilanes. Branched
vinylsilanes were employed with great efficacy in intermediates
in organic synthesis and their utility is mainly attributed to the
high regioselectivity obtained in reactions with electrophiles such
as Pd-catalyzed C-C bond formation reactions,21 also as
substrates for Tamao-Fleming oxidations22 and in Hiyama cross-
coupling reactions.23 To understand the regioselectivity of this
The dissociated Pd atoms from the Pd(PPh3)4 was confirmed with
ICP-AES and EDS analysis. After the fresh catalytic cycle, the
black particles was recovered by centrifuge method and washed
with water, ethanol and acetone and dried under vacuum. ICP-
AES analysis of the recovered black particles showed that 95.21
% Pd species were present in the recovered black material.
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The EDS spectrum (Fig. 6) of the recovered black material taken
at random points on the surface confirmed the presence of Pd
species. From this observation, it was clear that Pd metal present
in the inactive form needed activation for the subsequent recycle
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DOI: 10.1039/C7GC02869E
runs.
Table 4. The scope of Mizoroki-Heck cross-coupling of aryl bromides with olefinsa.
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DOI: 10.1039/C7GC02869E
aReaction conditions: aryl halides (1 mmol), olefins (1 mmol), Pd(PPh3)4 (2 mol %), Et3N (2 mmol), H2O (5 mL), 98 C, air, 3h. bIsolated
yields after column chromatography.
Table 5. The scope of Mizoroki-Heck cross-coupling of aryl chlorides with olefins.
In order to regain the activity of the spent catalyst, black Pd
particles were washed several times with water, methanol and
acetone and dried under vacuum. This was followed by
calcination at 600 C for 6h. To evaluate the chemical oxidation
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DOI: 10.1039/C7GC02869E
Figure 6. EDS of recovered black particles, Inset: centrifuged
black particles.
state of recovered Pd black material (Fig. 7a) and after calcined
Pd material (Fig. 7b), XPS was performed. The XPS analysis
provided useful information about the oxidation state of Pd. The
characteristic binding energy peak observed at 341.5, 340.7 eV
for electron transitions of Pd 3d3/2 of Pd0, and 335.4, 336.6 eV for
electron transitions of Pd 3d5/2 of Pd metal which clearly indicates
that the mixture of Pd(0) and Pd(II) present in recovered Pd black
material. The XPS analysis of calcinened Pd material showed the
binding energy peaks due to PdO, suggesting that the calcined
material existed in the Pd oxide state and also that PdO catalyst
was showed excellent catalytic activity with PPh3 as a ligand.
The calcined PdO metal examined for the next catalytic cycle for
the model reaction of 4-bromoanisole with t-butyl acrylate and in
presence of PPh3. As can be seen from the recycle results in
Figure 8, Pd catalyst showed excellent activity for ten runs with
no appreciable change in the product yield. These results proved
that the spent Pd catalyst could be revived by a simple protocol
Figure 7. XPS analysis of (a) recovered Pd black material and
(b) calcined Pd material.
making the process sustainable.
Conclusion
In conclusion, we developed efficient and environmentally sound
Mizoroki-Heck reaction in water under atmospheric conditions
without any additive. Initially, we used model reaction for
screening of various reaction parameters and then optimized
reaction conditions are extended for the wide range of functional
groups could be tolerated. This Pd(PPh3)4/Et3N/H2O catalytic
system showed high catalytic activity (TOF= 12 to 14 h-1) and
offers promising green development in terms of reaction time,
wide scope of applicability, good to excellent yields of the
desired products such as acrylate derivatives, operational
simplicity and with excellent recyclability of Pd-metal. We also
coupled unreactive aryl chlorides successfully under optimized
reaction conditions with moderate yield. The deactivation of
Pd(PPh3)4 catalyst during Mizoroki-Heck coupling reaction was
identified for the evolving a strategy to reuse the precious Pd-
metal for ten times without appreciable loss in its activity. This
water-compatible and air-stable catalytic protocol described here
provides a stepping stone towards a greener synthesis in
pharmaceutical and agrochemical industries.
Figure 8. Recyclability of Pd-metal in Mizoroki-Heck coupling
reaction.
Experimental section
Materials and General Methods. All the reagents were
commercially sourced from Sigma Aldrich and Spectrochem
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chemical companies and used as received. Solvents were dried
and purified by standard methods. Pd(PPh3)4, was obtained from
Sigma Aldrich and used without any pretreatment. H NMR and
13C NMR spectra were recorded on Bruker Avon 200 MHz or
500 MHz spectrometer using CDCl3 as solvent and TMS as
internal reference. Mass spectra were recorded on a Shimadzu
QP2010 GCMS instrument.
tert-butyl(E)-3-(4-nitrophenyl)acrylate (Table 4, entry 5): The
DOI: 10.1039/C7GC02869E
product was purified with column chromatography on silica gel
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1
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
92 % (184 mg); mp 146-148 C; 1H NMR (CDCl3, 200 MHz): 
8.34 (d, 2H, J=8.1 Hz), 7.60-7.71 (m, 3 H), 6.49 (d, 1H, J=16.0
Hz), 1.55 (s, 9 H); 13C NMR (CDCl3, 50MHz):  165.3, 148.3,
140.9, 140.6, 128.5, 124.6, 124.1, 81.4, 28.1 ppm; MS (ESI)
C13H15NO4: m/z 249.
Typical experimental procedure for the Mizoroki-Heck cross-
coupling reaction in water
butyl(E)-3-(4-nitrophenyl)acrylate (Table 4, entry 6): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
In a Schlenk flask, equipped with a magnetic stir bar, septum and
condenser, aryl halide (1.0mmol), olefin compound (1.0 mmol),
Et3N (2 mmol), Pd(PPh3)4 (2 mol%) and water (5mL) were
added. The flask was immersed in heating oil bath and reaction
mixture was stirred at 100 °C. Upon complete consumption of
starting materials as analysed by TLC (hexane:ethyl acetate, 8:2).
The resulting reaction mixture was extracted with diethyl ether
(3×10 mL). The combined organic layer was dried over
anhydrous Na2SO4 and concentrated to afford crude product
which was purified using column chromatography.
1
90 % (180 mg); mp 158-160 C; H NMR (200 MHz, CDCl3) 
8.31-8.22 (m, 2 H), 7.78-7.70 (m, 3 H), 6.57 (d, 1H, J = 16.0
Hz,), 4.24 (t, 2H, J = 6.6 Hz), 1.81- 1.72 (m, 2 H), 1.51 - 1.40 (m,
2 H), 0.97 (t, 3H, J = 7.3 Hz); 13C NMR (50 MHz, CDCl3) 
166.1, 148.5, 141.6, 140.6, 128.6, 128.4, 124.2, 122.6, 64.9, 30.7,
19.2, 13.7 ppm. MS (ESI) C13H15NO4: m/z 249.
ethyl(E)-3-(4-nitrophenyl)acrylate (Table 4, entry 7): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
tert-butyl(E)-3-(4-methoxyphenyl)acrylate (Table 4, entry 1): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a colorless oil: yield
1
82 % (164 mg); mp 152-154 C; H NMR (200MHz, CDCl3) 
8.35 (d, 2H, J = 8.7 Hz), 7.81- 7.73 (m, 3 H), 6.56 (d, 1H, J =
16.0 Hz), 4.30 (q, 2H, J = 7.1 Hz), 1.36 (t, 3H, J = 7.1 Hz); 13C
NMR (50 MHz, CDCl3)  166.0, 148.5, 141.6, 140.6, 128.6,
124.2, 122.6, 61.0, 14.3 ppm. MS (ESI) C11H11NO4: m/z 221.
methyl(E)-3-(4-nitrophenyl)acrylate (Table 4, entry 8): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
1
90% (168 mg); H NMR (200 MHz, CDCl3)  7.47 (d, 1 H, J =
15.9 Hz), 7.30 (d, 2H, J = 8.2 Hz), 7.07 (d, 2H, J = 7.8 Hz), 6.23
(d, 1H, J = 16.0 Hz), 2.30 (s, 3 H), 1.44 (s, 9 H); 13C NMR (50
MHz , CDCl3)  166.5, 143.6, 140.3, 131.9, 129.6, 129.3, 129.0,
128.5, 128.3, 128.0, 119.1, 80.3, 28.2, 21.4 ppm; MS (ESI)
C14H18O3: m/z 234.
1
84 % (168 mg); mp 180-182 C; H NMR (200MHz, CDCl3) 
butyl(E)-3-(4-methoxyphenyl)acrylate (Table 4, entry 2): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a colourless oil; yield
8.26 (d, 2H, J = 8.8 Hz), 7.77- 7.65 (m, 3 H), 6.56 (d, 1H, J =
16.0 Hz), 3.84 (s, 3 H). 13C NMR (50 MHz, CDCl3)  166.4,
148.5, 141.5, 141.9, 140.5, 128.6, 124.1, 122.1, 52.0 ppm; MS
(ESI) C10H9NO4: m/z 207.
1
91 % (171 mg); H NMR (200 MHz , CDCl3)  7.55 (d, 1H, J =
15.9 Hz), 7.45-7.40 (m, 2 H), 6.86- 6.80 (m, 2 H), 6.30 (d, 1H, J
= 15.9 Hz), 4.11 (t, 2H, J = 6.6 Hz), 3.73 (s, 3 H), 1.70-1.52 (m, 2
H), 1.46-1.30 (m, 2 H), 0.90 (t, 3H, J = 6.6 Hz); 13C NMR
(50MHz, CDCl3) 167.4, 161.3, 144.2, 129.7, 127.2, 115.8,
114.3, 64.2, 55.3, 30.8, 19.2, 13.8 ppm; MS (ESI) C14H18O3: m/z
234.
tert-butyl(E)-3-(p-tolyl)acrylate (Table 4, entry 9): The product
was purified with column chromatography on silica gel 60-120
mesh (hexane/ethyl acetate= 9:1) as a colorless oil; yield 90 %
1
(154 mg); H NMR (200 MHz, CDCl3)  7.44 (d, 1H, J = 16.0
Hz), 7.23 (d, 2H, J = 8.0 Hz), 6.99 (d, 2H, J = 6.0 Hz,), 6.19 (d,
1H, J = 16.0 Hz), 2.19 (s, 3 H), 1.41 (s, 9H); 13C NMR (50MHz,
CDCl3)  166.4, 143.5, 140.2, 131.9, 129.5, 127.9, 119.0, 80.1,
28.2, 21.3 ppm; MS (ESI) C14H18O2: m/z 218.
ethyl(E)-3-(4-methoxyphenyl)acrylate (Table 4, entry 3): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
butyl(E)-3-(p-tolyl)acrylate (Table 4, entry 10): The product was
purified with column chromatography on silica gel 60-120 mesh
(hexane/ethyl acetate= 9:1) as a colorless oil; yield 90 % (154
1
88 % (165 mg); mp 74-76C; H NMR (CDCl3, 200 MHz): 
7.55 (d, 1H, J=15.9 Hz), 7.40-7.43 (d, 2H, J=6 Hz), 6.81-6.84 (d,
2H, J=6 Hz), 6.21 (d, 1H, J=15.9 Hz), 4.16 (q, 2H, J=7.1 Hz),
3.73 (s, 3 H), 1.24 (t, 3H, J=7.1 Hz); 13C NMR (CDCl3, 50
MHz):  167.3, 161.3, 144.2, 129.7, 127.7, 127.2, 115.8, 114.3,
60.3, 55.3, 14.4 ppm; MS (ESI) C12H14O3: m/z 206.
1
mg); H NMR (200 MHz, CDCl3)  7.57 (d, 1H, J = 16.0 Hz),
7.37-7.26 (m, 2 H), 7.12-7.03 (m, 2 H), 6.30 (d, 1H, J = 16.0 Hz),
4.11 (t, 2H, J = 6.5 Hz), 2.3 (s, 3H), 1.59 (q, 2H, J = 6.9 Hz),
1.42-1.27 (m, 2 H), 0.88 (t, 3H, J = 8 Hz); 13C NMR (50MHz,
CDCl3)  167.3, 144.6, 140.6, 131.8, 129.6, 128.1, 117.2, 30.8,
21.4, 19.2, 13.8 ppm. MS (ESI) C14H18O2: m/z 218.
methyl(E)-3-(4-methoxyphenyl)acrylate (Table 4, entry 4): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
ethyl(E)-3-(p-tolyl)acrylate (Table 4, entry 11): The product was
purified with column chromatography on silica gel 60-120 mesh
(hexane/ethyl acetate= 9:1) as a colorless oil; yield 86 % (147
1
85 % (160 mg); mp 90-92C; H NMR (CDCl3, 200 MHz): 
7.65 (d, 1H, J=16.0 Hz), 7.47 (d, 2H, J=8.0 Hz), 6.90 (d, 2H,
J=8.1 Hz), 6.31 (d,1H, J=16.0 Hz), 3.83 (s, 3 H), 3.79 (s, 3 H);
13C NMR (CDCl3, 50 MHz):  167.7, 161.4, 144.5, 129.7, 127.1,
118.2, 114.3, 55.3, 51.5 ppm. MS (ESI) C11H12O3: m/z 192.
1
mg); H NMR (200MHz , CDCl3)  7.59 (d, 1H, J = 16.0 Hz),
7.40-7.30 (m, 2 H), 7.20-7.11 (m, 2 H), 6.32 (d, 1H, J = 15.9 Hz),
4.18 (q, 2H, J = 7.2 Hz), 2.30 (s, 3 H), 1.26 (t, 3H, J = 7.1 Hz);
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Green Chemistry
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ARTICLE
13C NMR (50MHz, CDCl3)  167.2, 144.6, 140.6, 131.8, 129.6,
128.1, 117.2, 60.4, 21.5, 14.4 ppm. MS (ESI) C12H14O2: m/z 190.
methyl(E)-3-(p-tolyl)acrylate (Table 4, entry 12): The product
was purified with column chromatography on silica gel 60-120
mesh (hexane/ethyl acetate= 9:1) as a colorless oil; yield 88 %
6.98-6.90 (m, 2 H), 6.29-6.21 (m, 1 H), 4.15-4.03 (m, 2 H), 1.61 -
DOI: 10.1039/C7GC02869E
1.51 (m, 2 H), 1.39 - 1.15 (m, 2 H), 0.98-0.80 (m, 3 H); C NMR
View Article Online
13
(50 MHz, CDCl3)  166.6, 161.2, 143.0, 130.7, 129.9, 118.0,
116.0, 115.6, 64.2, 30.7, 19.1, 13.6 ppm. MS (ESI) C13H15FO2:
m/z 222.
1
ethyl(E)-3-(4-fluorophenyl)acrylate (Table 4, entry 19): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a colorless oil; yield
(150 mg); H NMR (200MHz , CDCl3) 7.67 (d, 1H, J = 16.0
Hz), 7.42 (d, 2H, J 8.0 Hz), 7.18 (d, 2H, J = 8.0 Hz), 6.39 (d, 1H,
J =16.0 Hz), 3.79 (s, 3 H), 2.37 (s, 3 H); 13C NMR (50MHz,
CDCl3)  167.6, 144.9, 140.7, 131.6, 129.6, 128.0, 116.7, 51.6,
21.4 ppm MS (ESI) C11H12O2: m/z 176.
1
80 % (140 mg); H NMR (200 MHz, CDCl3)  7.65-7.41 (m,
3H), 7.15-70 (m, 2 H), 6.43 - 6.29 (m, 1 H), 4.30-4.11 (m, 2 H),
1.33-1.27 (m, 3 H); 13C NMR (50 MHz, CDCl3)  166.5, 161.2,
142.9, 130.7, 129.9, 129.7, 128.7, 127.9, 117.9, 116.0, 115.6,
60.3, 14.1 ppm. MS (ESI) C11H11FO2: m/z 194.
tert-butyl(E)-3-(4-chlorophenyl)acrylate (Table 4, entry 13): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
1
methyl(E)-3-(4-fluorophenyl)acrylate (Table 4, entry 20): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow oil; yield 81
91 % (174 mg); mp 158-160 C; H NMR (200 MHz, CDCl3)
7.53 (d, 1H, J = 16.0 Hz), 7.57 - 7.30 (m, 4 H), 6.34 (d, 1H, J =
15.9 Hz), 1.53 (s, 9 H); 13C NMR (50 MHz, CDCl3)  166.0,
142.1, 135.8, 133.2, 129.1, 128.6, 120.8, 80.7, 28.2 ppm. MS
(ESI) C13H15ClO2: m/z 238.
1
% (142 mg); H NMR (200 MHz, CDCl3)  7.57 (d, J=16.0 Hz,
1H), 7.46-7.39 (m, 2 H), 7.03-6.95 (m, 2H), 6.28 (d, J=16.0, 1
H), 3.72 (s, 3 H). 13C NMR (50 MHz, CDCl3)  167.2, 161.4,
143.5, 130.0, 129.8, 117.5, 116.2, 115.8, 51.7 ppm. MS (ESI)
C10H9FO2: m/z 180.
tert-butyl(E)-3-(thiophen-3-yl)acrylate (Table 4, entry 21): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a purple oil; yield 93
% (152 mg); 1H NMR (200 MHz, CDCl3)  7.60 (d, 1H, J = 15.7
Hz), 7.23 (d, 1H, J = 5.1 Hz), 7.12-7.08 (m, 1 H), 6.94-6.90 (m, 1
H), 6.09 (d, 1H, J = 15.7 Hz), 1.43 (s, 9 H). 13C NMR (50 MHz,
CDCl3) 166.1, 139.8, 136.1, 130.5, 128.0, 124.4, 123.8, 119.1,
80.5, 28.2 ppm. MS (ESI) C11H14SO2: m/z 210.
butyl(E)-3-(thiophen-3-yl)acrylate (Table 4, entry 22): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow oil; yield 90
% (148 mg). 1H NMR (200 MHz , CDCl3)  7.79 (d, 1H, J = 15.7
Hz), 7.37 (d, 1H, J = 4.9 Hz), 7.26-7.03 (m., 1 H), 6.95 (dd, 1H, J
= 3.7, 4.9 Hz), 6.15 (d, 1H, J = 15.7 Hz), 4.10 (t, 2H, J = 6.6 Hz),
1.78 - 1.60 (m, 2H), 1.41-1.38 (m, 2 H), 0.88 (t, 3H, J = 6.6 Hz).
13C NMR (50 MHz, CDCl3)  166.9, 139.6, 137.0, 130.8, 128.7,
128.3, 128.1, 117.1, 64.4, 30.8, 19.2, 13.8 ppm. MS (ESI)
C11H14SO2: m/z 210.
ethyl(E)-3-(thiophen-3-yl)acrylate (Table 4, entry 23): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a purple oil; yield 89
% (145 mg); 1H NMR (200 MHz , CDCl3)  7.71 (d, 1H, J = 15.8
Hz), 7.29 (d, 1H, J = 5.1 Hz), 7.17 (d, 1H, J = 4.0 Hz), 6.97 (dd,
1H, J = 3.7, 5.1 Hz), 6.16 (d, 1H, J = 15.7 Hz), 4.23 - 4.12 (m, 2
H), 1.27 (t, 3H, J =6.6 Hz); 13C NMR (50 MHz, CDCl3)  166.9,
139.6, 137.0, 130.8, 128.4, 128.1, 117.1, 60.5, 14.3 ppm. MS
(ESI) C9H10SO2: m/z 182.
butyl(E)-3-(4-chlorophenyl)acrylate (Table 4, entry 14): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow oil; yield 90
% (172 mg); 1H NMR (200 MHz, CDCl3)  7.52 (d, 1H, J = 15.9
Hz), 7.34 (d, 2H, J = 8.6 Hz), 7.23 (d, 2H, J = 8.6 Hz), 6.30 (d,
1H, J = 16.0 Hz), 4.11 (t, 2H, J = 6.6 Hz), 1.65 - 1.50 (m, 2 H),
1.41-1.33 (m, 2 H), 0.86 (t, 3H, J = 7.3 Hz); 13C NMR (50 MHz,
CDCl3)  166.7, 143.0, 136.1, 133.0, 129.7, 129.2, 129.1, 128.2,
118.9, 64.5, 30.8, 19.2, 13.7 ppm. MS (ESI) C13H15ClO2: m/z
238.
ethyl(E)-3-(4-chlorophenyl)acrylate (Table 4, entry 15): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow oil; yield 85
% (162 mg); 1H NMR (200 MHz, CDCl3)  7.52 (d, 1H, J = 16.0
Hz), 7.40-7.21 (m, 4 H), 6.30 (d, 1H, J = 16.0 Hz), 4.12 (t, 2H, J
= 6.6 Hz), 1.24 (t, 3H, J=7.1 Hz); 13C NMR (50 MHz, CDCl3) 
166.6, 143.0, 136.1, 133.0, 129.2, 128.2, 118.9, 60.6, 14.3 ppm.
MS (ESI) C11H11ClO2: m/z 210.
methyl(E)-3-(4-chlorophenyl)acrylate (Table 4, entry 16): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate=9:1) as a yellow solid; yield
1
85 % (162 mg); mp 82-84 C; H NMR (200 MHz, CDCl3) 
7.74 (d, 1H, J = 15.9 Hz), 7.57-7.42 (m, 4 H), 6.48 (d, 1H, J =
16.0 Hz), 3.82 (s, 3 H); 13C NMR (50 MHz, CDCl3)  167.2,
143.4, 136.2, 132.9, 129.2, 128.1, 118.4, 51.8 ppm. MS (ESI)
C10H9ClO2: m/z 196.
tert-butyl(E)-3-(4-fluorophenyl)acrylate (Table 4, entry 17): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow oil; yield 90
1
% (158 mg); H NMR (200 MHz, CDCl3)  7.45-7.37 (m, 3 H),
6.95-6.82 (m, 2 H), 6.13 (d, 1H, J = 16.0 Hz), 1.40 (s, 9 H). 13C
NMR (50 MHz, CDCl3)  165.9, 161.1, 142.1, 130.9, 130.8,
129.8, 129.6, 119.9, 116.0, 115.6, 80.3, 27.7 ppm; MS (ESI)
C13H15FO2: m/z 222.
methyl(E)-3-(thiophen-3-yl)acrylate (Table 4, entry 24): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a purple oil; yield 88
% (144 mg). 1H NMR (200 MHz, CDCl3)  7.71 (d, 1H, J = 15.7
Hz), 7.29 (d, 1H, J = 5.1 Hz), 7.17 (d, 1H, J = 3.5 Hz), 7.29-6.92
(m, 1 H), 6.16 (d, 1H, J = 15.8 Hz), 3.71 (s, 3 H); 13C NMR (50
MHz, CDCl3)  167.3, 139.5, 137.3, 131.0, 128.5, 128.1, 127.8,
124.4, 123.8, 116.6, 51.7 ppm. MS (ESI) C8H8SO2: m/z 168.
butyl(E)-3-(4-fluorophenyl)acrylate (Table 4, entry 18): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow oil; yield 90
1
% (158 mg); H NMR (200 MHz, CDCl3)  7.48-7.32 (m, 3 H),
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J. Name., 2013, 00, 1-3 | 9
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ARTICLE
Journal Name
tert-butyl(E)-3-([1,1'-biphenyl]-4-yl)acrylate (Table 4, entry 25):
The product was purified with column chromatography on silica
gel 60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid;
yield 90 % (209 mg); mp 134-136 C; 1H NMR (200 MHz,
CDCl3)  7.78 - 7.55 (m, 7 H), 7.49- 7.45 (m, 3 H), 6.40 (d, 1H, J
= 15.9 Hz), 1.55 (s, 9 H); 13C NMR (50 MHz, CDCl3)  166.4,
143.1, 142.7, 140.3, 133.7, 128.9, 128.5, 127.8, 127.5, 127.1,
126.6, 120.1, 80.6, 28.3 ppm. MS (ESI) C19H20O2: m/z 280.
butyl(E)-3-([1,1'-biphenyl]-4-yl)acrylate (Table 4, entry 26): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
ethyl(E)-3-(4-benzoylphenyl)acrylate (Table 4, entry 31): The
DOI: 10.1039/C7GC02869E
product was purified with column chromatography on silica gel
View Article Online
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
1
83 % (217 mg); mp 80-82 C; H NMR (200 MHz, CDCl3) 
7.85- 7.79 (m, 4 H), 7.78- 7.65 (m, 4 H), 7.61 - 7.50 (m, 2 H),
6.54 (d, 1H, J = 16.0 Hz), 4.35-4.24 (q, 2 H), 1.36 (t, 3H, J = 6.6
Hz); 13C NMR (50 MHz, CDCl3)  195.8, 166.5, 143.1, 138.6,
138.2, 137.3, 132.6, 130.5, 129.9, 128.4, 127.8, 120.7, 60.7, 14.3
ppm. MS (ESI) C18H16O3: m/z 280.
methyl(E)-3-(4-benzoylphenyl)acrylate (Table 4, entry 32): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
1
92 % (214 mg); mp 118-120 C; H NMR (200 MHz, CDCl3) 
1
84 % (219 mg); mp 150-152 C; H NMR (200 MHz, CDCl3) 
7.78-7.57 (s., 7 H), 7.31 (d, 3H, J = 7.7 Hz), 6.36 (d, 1H, J = 15.9
Hz), 4.11 (t, 2H, J = 5.6 Hz), 1.65 - 1.53 (m, 2 H), 1.41-1.28 (m,
2 H), 0.87 (t, 3H, J = 6.7 Hz); 13C NMR (50MHz, CDCl3) 
167.0, 143.9, 142.8, 140.0, 133.3, 128.8, 128.4, 127.7, 127.4,
126.9, 126.5, 118.0, 64.3, 30.7, 19.1, 13.7 ppm. MS (ESI)
C19H20O2: m/z 280.
7.98-7.76 (m, 5H), 7.74-7.58 (m, 4 H), 7.52 (d, 2H, J = 7.5 Hz),
6.56 (d, 1H, J = 16.0 Hz), 3.84 (s, 3 H); 13C NMR (50 MHz,
CDCl3)  195.8, 166.9, 143.4, 138.1, 132.6, 130.6, 130.0, 128.4,
127.8, 120.2, 51.9 ppm. MS (ESI) C17H14O3: m/z 266.
tert-butyl(E)-3-(naphthalen-1-yl)acrylate (Table 4, entry 33):
The product was purified with column chromatography on silica
gel 60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow oil;
ethyl(E)-3-([1,1'-biphenyl]-4-yl)acrylate (Table 4, entry 27): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
1
yield 89 % (184 mg); H NMR (200 MHz, CDCl3)  8.56-8.48
1
(d, 1H, J= 16.0 Hz), 8.11 (s, 1H), 7.85-7.68 (m, 7H), 7.50-7.39
(m, 7H), 6.57-6.47 (m, 2 H), 1.63 (s, 18 H); 13C NMR (50 MHz,
CDCl3)  166.1, 143.6, 140.4, 134.1, 133.7, 133.3, 132.1, 131.8,
131.4, 129.7, 128.6, 127.8, 123.5, 120.4, 80.1, 28.3 ppm; MS
(ESI) C17H18O2: m/z 254.
84 % (196 mg); mp 90-92 C; H NMR (200 MHz, CDCl3) 
7.80-7.56 (m, 7 H), 7.49-7.36 (m, 3 H), 6.47 (d, 1H, J = 15.9 Hz),
4.28 (q, 2H, J = 7.1 Hz), 1.35 (t, 3H, J = 7.1 Hz); 13C NMR (50
MHz, CDCl3) 167.1, 144.1, 143.0, 140.2, 133.5, 128.9, 128.6,
127.9, 127.6, 127.1, 118.2, 60.6, 14.4 ppm. MS (ESI) C17H16O2:
m/z 252.
methyl(E)-3-([1,1'-biphenyl]-4-yl)acrylate (Table 4, entry 28):
The product was purified with column chromatography on silica
gel 60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid;
Yield 86 % (200 mg); mp 176-178 C; 1H NMR (200 MHz,
CDCl3)  7.74 (d, J = 16.0 Hz, 1 H), 7.63-7.59 (m, 6H), 7.46-
7.37 (m, 3 H), 6.48 (d, J = 16.0 Hz, 1 H), 3.82 (s, 3 H). 13C NMR
(50 MHz, CDCl3)  167.4, 144.4, 143.0, 140.1, 133.3, 128.9,
128.6, 128.6, 127.5, 127.0 117.6, 51.7 ppm; MS (ESI) C16H14O2:
m/z 238.
tert-butyl(E)-3-(4-benzoylphenyl)acrylate (Table 4, entry 29):
The product was purified with column chromatography on silica
gel 60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid;
yield 90 % (235 mg); mp 96-98 C; 1H NMR (200 MHz, CDCl3)
 7.84-7.76 (m, 4 H), 7.68-7.56 (m, 4 H), 7.53 - 7.43 (m, 2 H),
6.48 (d, 1H, J = 15.9 Hz), 1.55 (s, 9 H); 13C NMR (50 MHz,
CDCl3)  196.0, 165.9, 142.1, 138.5, 137.4, 132.6, 130.6, 130.0,
128.4, 127.7, 122.6, 81.0, 28.2 ppm; MS (ESI) C20H20O3: m/z
308.
butyl(E)-3-(naphthalen-1-yl)acrylate (Table 4, entry 34): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
1
90% (186 mg); mp 52-54 C; H NMR (200 MHz, CDCl3) 
8.51-8.43 (d, 1H, J=16.0 Hz), 8.11-8.06 (d, 1H, J=9.3 Hz), 7.76-
7.63 (m, 7H), 7.52-7.36 (m, 7H), 6.51-6.41 (dd, 2H, J = 8.0, 16.0
Hz), 4.25-4.16 (m, 4 H), 1.69-1.58 (m, 4 H), 1.46-1.35 (m, 4H),
0.93 (t, 6H, J = 7.3 Hz); 13C NMR (50 MHz, CDCl3)  167.1,
144.6, 141.5, 132.0, 129.9, 128.6, 128.5, 127.8, 126.7, 123.5,
118.4, 64.4, 30.8, 19.3, 13.8 ppm; MS (ESI) C17H18O2: m/z 254.
ethyl(E)-3-(naphthalen-1-yl)acrylate (Table 4, entry 35): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow oil; yield 85
1
% (176 mg); H NMR (200 MHz, CDCl3)  8.38-830 (d, 1H,
J=16.0 Hz), 7.98 (d, 1H, J=8.0 Hz), 7.63-7.54 (m, 7H), 7.48-7.25
(m, 7H), 6.38-6.29 (dd, 2H, J = 8.0, 16.0 Hz), 4.19-4.09 (m, 4 H),
1.22-1.14 (m, 6 H); 13C NMR (50 MHz, CDCl3)  167.0, 144.6,
133.3, 129.9, 128.7, 128.5, 127.8, 127.2, 126.8, 126.6, 123.5,
118.4, 60.5, 14.4 ppm; MS (ESI) C15H14O2: m/z 226.
methyl(E)-3-(naphthalen-1-yl)acrylate (Table 4, entry 36): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
butyl(E)-3-(4-benzoylphenyl)acrylate (Table 4, entry 30): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
1
1
82 % (170 mg); mp 88-90 C; H NMR (200 MHz, CDCl3) 
90% (235 mg); mp 56-58 C; H NMR (200 MHz, CDCl3) 
8.51 (d, 1H, J = 16.0 Hz), 8.16 (d, 1H, J = 8.0 Hz), 7.86-7.75 (m,
7H), 7.62- 7.42 (m, 7H), 6.56-6.46 (dd, 2H, J = 8.0, 16.0 Hz),
3.83 (s, 3 H), 3.81 (s, 3 H); 13C NMR (50 MHz, CDCl3)  167.5,
144.9, 141.9, 134.3, 130.6, 130.0, 128.7, 127.8, 127.3, 126.7,
125.0, 123.5, 118.0, 51.8 ppm; MS (ESI) C14H12O2: m/z 212.
tert-butyl(E)-3-(4-acetylphenyl)acrylate (Table 4, entry 37): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a colorless solid;
7.78- 7.62 (m, 5 H), 7.60 - 7.49 (m, 3 H), 7.45 - 7.34 (m, 2 H),
6.45 (d, 1H, J = 16.0 Hz), 4.13 (t, 2H, J = 6.6 Hz), 1.72 - 1.49 (m,
2 H), 1.43-1.35 (m, 2 H), 0.88 (t, 3H, J = 6.6 Hz); 13C NMR (50
MHz, CDCl3)  195.8, 166.6, 143.0, 138.6, 138.1, 132.6, 130.5,
129.9, 128.3, 127.7, 120.6, 64.6, 30.7, 19.1, 13.7 ppm; MS (ESI)
C20H20O3: m/z 308.
10 | J. Name., 2012, 00, 1-3
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ARTICLE
yield 91 % (181 mg); mp 120-122 C; 1H NMR (200 MHz,
CDCl3)  7.87 (d, 2H, J = 8.3 Hz,), 7.59 -7.54 (m, 3 H), 6.37 (d,
1H, J = 16.0 Hz), 2.52 (s, 3 H), 1.56 (s, 9 H); 13C NMR (50 MHz,
CDCl3)  197.3, 165.7, 141.9, 139.0, 137.8, 128.8, 128.0, 122.8,
80.9, 28.2, 26.7 ppm; MS (ESI) C15H18O3: m/z 246.
MHz, CDCl3)  167.4, 161.3, 144.2, 129.6, 127.2, 115.8, 64.2,
View Article Online
55.3, 30.8, 19.2, 13.7; MS (ESI) C14H18OD3:OmI:/1z02.130439. /C7GC02869E
ethyl(E)-3-(4-methoxyphenyl)acrylate (Table 5, entry 3): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
45 % (64 mg); mp 74-76 C; 1H NMR (200 MHz, CDCl3)  7.54
(d, 1H, J=16 Hz), 7.36 (d, 2H, J=10 Hz), 6.79 (d, 2H, J=8 Hz),
6.21 (d, 1H, J=16 Hz), 4.15 (q, 2H, J=7.0 Hz), 3.72 (s, 3 H), 1.23
ppm (t, 3H, J=7.0 Hz); 13C NMR (CDCl3, 50 MHz)  167.3,
161.4, 144.2, 129.6, 127.2, 115.7, 114.3, 60.3, 55.3, 14.4 ppm;
MS (ESI) C12H14O3: m/z 206.
butyl(E)-3-(4-acetylphenyl)acrylate (Table 4, entry 38): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a colorless oil; yield
1
92 % (183 mg); H NMR (200 MHz, CDCl3)  7.98 (d, 2H, J =
8.3 Hz), 7.61 (d, 1H, J = 16.0 Hz), 7.52 (d, 2H, J = 8.3 Hz), 6.44
(d, 1H, J = 16.0 Hz), 4.14 (t, 2H, J = 6.6 Hz), 2.53 (s, 3 H), 1.69 -
1.53 (m, 2 H), 1.49-1.36 (m, 2 H), 0.88 (t, 3H, J = 7.3 Hz); 13C
NMR (50 MHz, CDCl3)  197.3, 166.6, 143.0, 138.8, 138.0,
128.9, 128.1, 120.9, 64.7, 30.7, 26.7, 19.2, 13.7 ppm; MS (ESI)
C15H18O3: m/z 246.
methyl(E)-3-(4-methoxyphenyl)acrylate (Table 5, entry 4): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
44 % (63 mg); mp 90-92 C; 1H NMR (200 MHz, CDCl3)  7.64
(d, 1H, J=16.0 Hz), 7.48 (d, 2H, J=8.0 Hz), 6.90 (d, 2H, J=10
Hz), 6.31 (d, 1H, J=16.0 Hz), 3.84 (s, 3 H), 3.79 (s, 3 H); 13C
NMR (50 MHz, CDCl3)  167.7, 161.4, 144.5, 129.7, 127.2,
115.3, 114.3, 55.3, 51.5 ppm; MS (ESI) C13H15NO4: m/z 249.
tert-butyl(E)-3-(4-nitrophenyl)acrylate (Table 5, entry 5): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
ethyl(E)-3-(4-acetylphenyl)acrylate (Table 4, entry 39): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
1
86 % (171 mg); mp 46-48 C; H NMR (200 MHz, CDCl3) 
7.86 (d, 2H, J = 8.3 Hz), 7.58 (d, 1H, J = 16.2 Hz), 7.49 (d, 2H, J
= 8.3 Hz), 6.41 (d, 1H, J = 16.0 Hz), 4.17 (q, 2H, J = 7.1 Hz),
2.50 (s, 3 H), 1.24 (t, 3H, J = 7.1 Hz); 13C NMR (50 MHz,
CDCl3)  197.2, 166.4, 142.9, 138.7, 137.9, 128.8, 128.1, 120.8,
60.7, 26.6, 14.3 ppm; MS (ESI) C13H14O3: m/z 218.
methyl(E)-3-(4-acetylphenyl)acrylate (Table 4, entry 40): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
83 % (165 mg); mp 114-116 C; 1H NMR (200 MHz, CDCl3) 
8.0 (d, 2H, J = 8.2 Hz), 7.71 (d, 1H, J = 16.0 Hz), 7.61 (d, 2H, J
= 8.2 HzH), 6.53 (d, 1H, J = 16.0 Hz), 3.83 (s, 3 H), 2.62 (s, 3
H); 13C NMR (50 MHz, CDCl3)  197.3, 166.9, 143.3, 138.7,
138.1, 128.9, 128.2, 120.4, 51.9, 26.7 ppm; MS (ESI) C12H12O3:
m/z 204.
1
41 % (64 mg); mp 146-148 C; H NMR (200 MHz, CDCl3) 
8.16 (d, 2 H, J= 8.1Hz), 7.60-7.50 (m, 3 H), 6.42 (d, 1H, J=16.0
Hz), 1.47 (s, 9 H); 13C NMR (50MHz, CDCl3)  165.2, 148.3,
140.8, 140.5, 128.5, 124.5, 124.1, 81.3, 28.1 ppm; MS (ESI)
C13H15NO4: m/z 249.
butyl(E)-3-(4-nitrophenyl)acrylate (Table 5, entry 6): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
1
43 % (68 mg); mp 158-160 C; H NMR (200 MHz, CDCl3) 
8.25 (d, 2H, J = 8.0 Hz), 7.75-7.66 (m, 3 H), 6.57 (d, 1H, J = 16.0
Hz), 4.24 (t, 2H, J = 6.6 Hz), 1.74-1.64 (m, 2 H), 1.50 - 1.39 (m,
2 H), 0.97 (t, 3H, J = 8.0 Hz); 13C NMR (50 MHz, CDCl3) 
166.1, 148.4, 141.5, 140.6, 128.6, 128.4, 124.1, 122.6, 64.9, 30.7,
19.1, 13.7 ppm; MS (ESI) C13H15NO4: m/z 249.
(E)-trimethyl(3-(p-tolyl)allyl)silane (Scheme 1 ): The product
was purified with column chromatography on silica gel 60-120
mesh (hexane/ethyl acetate= 9:1) as a colorless oil; yield 79 %
1
ethyl(E)-3-(4-nitrophenyl)acrylate (Table 5, entry 7): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a yellow solid; yield
(135 mg); H NMR (200 MHz, CDCl3)  7.29 (d, 4H, J = 8.1
Hz), 7.16 (d, 4H, J = 8.0 Hz), 6.36 - 6.25 (m, 4 H), 2.39 (s, 6 H),
1.75- 1.71 (m, 4 H), 0.13 (s, 18 H); 13C NMR (50 MHz, CDCl3) 
138.1, 131.5, 130.5, 129.0, 127.8, 26.2, 23.4, 0.5 ppm; MS (ESI)
C13H20Si: m/z 204.
1
46 % (72 mg); mp 152-154 C; H NMR (200MHz, CDCl3) 
8.25 (d, 2H, J = 8.0 Hz), 7.75- 7.65 (m, 3 H), 6.56 (d, 1H, J =
16.0 Hz), 4.30 (q, 2H, J = 7.20 Hz), 1.36 (t, 3H, J = 7.20 Hz); 13
C
tert-butyl(E)-3-(4-methoxyphenyl)acrylate (Table 5, entry 1): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a colorless oil; yield
NMR (50 MHz, CDCl3)  166.0, 148.5, 141.6, 140.6, 128.6,
124.2, 122.6, 61.0, 14.3 ppm; MS (ESI) C11H11NO4: m/z 221.
methyl(E)-3-(4-nitrophenyl)acrylate (Table 5, entry 8): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
1
40 % (57 mg); H NMR (200MHz, CDCl3) 7.48 (d, 1H, J=14
Hz), 7.32 (d, 2H, J=8.0 Hz), 7.09 (d, 2H, J=8.0 Hz), 6.24 (d, 1H,
J=16.0 Hz), 2.28 (s, 3 H), 1.45 (s, 9 H); 13C NMR (50 MHz,
CDCl3) 166.5, 143.5, 140.3, 132.0, 129.5, 127.9, 119.1, 80.3,
28.2, 21.4. MS (ESI) C14H18O3: m/z 234.
butyl(E)-3-(4-methoxyphenyl)acrylate (Table 5, entry 2): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a colorless oil; yield
42 % (60 mg); 1H NMR (200 MHz, CDCl3)  7.55 (d, 1H, J=16.0
Hz), 7.38 (d, 2H, J=8.0 Hz), 6.83 (d,2H, J=10 Hz), 6.31 (d, 1H,
J=16.0 Hz), 4.11 (t, 3H, J=4.66 Hz) 3.73 (s, 3 H), 1.63-1.53 (m, 2
H), 1.40-1.29 (m, 2 H), 0.87 (t, 3H, J = 4.6 Hz); 13C NMR (50
1
40 % (63 mg); mp 180182 C; H NMR (200 MHz, CDCl3) 
7.25 (d, 1H, J=8.0 Hz), 7.77-7.65 (m, 3 H), 6.56 (d, 1H, J=16.0
Hz), 3.84 (s, 3 H); 13C NMR (50 MHz, CDCl3)  166.4, 148.5,
141.9, 140.5, 128.6, 124.2, 122.1, 52.0 ppm; MS (ESI)
C10H9NO4: m/z 207.
tert-butyl(E)-3-(4-benzoylphenyl)acrylate (Table 5, entry 9): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
43 % (93 mg); mp 96-98 C; 1H NMR (200 MHz, CDCl3)  7.84-
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
ed. (Eds.: A. de Meijere, F. Die-derich), Wiley-VCH,
7.82 (m, 4 H), 7.79-7.77 (m, 4 H), 7.63- 7.49 (m, 2 H), 6.48 (d,
1H, J = 16.0 Hz), 1.55 (s, 9 H); 13C NMR (50 MHz, CDCl3) 
195.9, 165.8, 142.1, 138.5, 137.3, 132.6, 130.5, 130.0, 128.3,
127.7, 122.6, 81.0, 28.1 ppm; MS (ESI) C20H20O3: m/z 308.
butyl(E)-3-(4-benzoylphenyl)acrylate (Table 5, entry 10): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
45 % (97 mg); mp 56-58 C; 1H NMR (200 MHz, CDCl3)  7.85-
7.77 (m, 4 H), 7.69 - 7.58 (m, 4 H), 7.53 - 7.45 (m, 2 H), 6.55 (d,
1H, J = 16.0 Hz), 4.24 (t, 2H, J = 4.66 Hz), 1.75 - 1.64 (m, 2 H),
1.62-1.43 (m, 2H), 0.97 (t, 3H, J=4.66 Hz); 13C NMR (50 MHz,
CDCl3)  195.9, 166.6, 143.1, 138.6, 138.2, 132.6, 130.5, 130.0,
128.4, 127.8, 120.7, 64.7, 30.7, 19.21, 13.7 ppm; MS (ESI)
C20H20O3: m/z 308.
ethyl(E)-3-(4-benzoylphenyl)acrylate (Table 5, entry 11): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
40 % (86 mg); mp 80-82 C; 1H NMR (200 MHz, CDCl3) 
7.85- 7.81 (m, 4H), 7.78 - 7.65 (m, 4H), 7.61- 7.49 (m, 2 H), 6.54
(d, 1H, J = 16.0 Hz), 4.29 (q, 2H, J = 7.20 Hz), 1.36 (t, 3H, J =
7.20 Hz); 13C NMR (50 MHz, CDCl3)  195.8, 166.5, 143.5,
138.7, 138.2, 137.3, 132.6, 130.5, 130.0, 128.4, 127.8, 120.7,
60.7, 14.3 ppm; MS (ESI) C18H16O3: m/z 280.
View Article Online
DOI: 10.1039/C7GC02869E
Weinheim, 2004; (c) M. Beller, Zapf, A. Handbook of
Organopalladium Chemistry for Organic Synthesis, Vol. 1
(Ed.: E.-I. Negishi), Wiley, New York, 2002, pp.1209–
1222.
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5563.
methyl(E)-3-(4-benzoylphenyl)acrylate (Table 5, entry 12): The
product was purified with column chromatography on silica gel
60-120 mesh (hexane/ethyl acetate= 9:1) as a white solid; yield
49 % (106 mg); mp 150-152 C; 1H NMR (200 MHz, CDCl3) 
7.85-7.78 (m, 4H), 7.78-7.65 (m, 4 H), 7.61-7.51 (m, 2 H), 6.55
(d, 1H, J = 16.0 Hz), 3.83 (s, 3 H); 13C NMR (50 MHz, CDCl3) 
195.8, 166.9, 143.4, 138.7, 138.1, 137.3, 132.6, 130.5, 130.0,
128.4, 127.8, 120.7, 51.9 ppm; MS (ESI) C17H14O3: m/z 266.
(a) Y. Wan, H. Wang, Q. Zhao, M. Klingstedt, O. Terasaki
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One of the authors Sanjay Jadhav is grateful to the Science &
Engineering Research Board, Department of Science and
Technology (SERB-DST), New Delhi, Government of India, for
the award of the National Post-Doctoral Fellow (N-PDF; File No.
PDF/2015/000569).
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Notes and References
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12 | J. Name., 2012, 00, 1-3
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15 (a) S. Jadhav, A. Kumbhar and R. Salunkhe, Appl.
Organometal. Chem., 2015, 29,339;(b) M.R.Shaaban, A. F.
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DOI: 10.1039/C7GC02869E
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Green Chemistry
Page 14 of 14
View Article Online
DOI: 10.1039/C7GC02869E
An Efficient Palladium Catalyzed Mizoroki-Heck Cross-
Coupling in Water
Sanjay N. Jadhav, Chandrashekhar V. Rode*
Chemical Engineering and Process Development Division, CSIR—National Chemical
Laboratory, Pune 411008, M. S. India.
E-mail: cv.rode@ncl.res.in
Graphical Abstract