Palladium-catalyzed decarboxylative coupling of α,β-unsaturated carboxylic acids with aryl tosylates

Article abstract of DOI:10.1002/aoc.4914

We report a general method for selective cross-coupling of α,β-unsaturated carboxylic acids with aryl tosylates enabled by versatile Pd(II) complexes. This method features the general cross-coupling of ubiquitous α,β-unsaturated carboxylic acids by decarboxylation. The transformation is characterized by its operational simplicity, the use of inexpensive, air-stable Pd(II) catalysts, scalability and wide substrate scope. The reaction proceeds with high trans selectivity to furnish valuable (E)-1,2-diarylethenes.

Full text of DOI:10.1002/aoc.4914

Received: 28 December 2018
DOI: 10.1002/aoc.4914
Revised: 26 February 2019
Accepted: 27 February 2019
C O M M U N I C A T I O N
Palladium‐catalyzed decarboxylative coupling of
α,β‐unsaturated carboxylic acids with aryl tosylates
Wei Zhang
| Gairong Chen | Kaikai Wang | Ran Xia
Department of Chemistry and Chemical
Engineering, Xinxiang University,
Xinxiang 453003, China
We report a general method for selective cross‐coupling of α,β‐unsaturated car-
boxylic acids with aryl tosylates enabled by versatile Pd(II) complexes. This
method features the general cross‐coupling of ubiquitous α,β‐unsaturated car-
boxylic acids by decarboxylation. The transformation is characterized by its
operational simplicity, the use of inexpensive, air‐stable Pd(II) catalysts, scal-
ability and wide substrate scope. The reaction proceeds with high trans selec-
tivity to furnish valuable (E)‐1,2‐diarylethenes.
Correspondence
Wei Zhang, Department of Chemistry and
Chemical Engineering, Xinxiang
University, Xinxiang 453003, China.
Email: xinxiangzhangwei@126.com
Funding information
National Natural Science Foundation of
China, Grant/Award Number: 21602189;
Program for Science and Technology
Development of Henan Province, Grant/
Award Number: 182102311119
KEYWORDS
aryl tosylates, decarboxylative coupling, palladium‐catalyzed, synthesis of trans‐vinylarene, α,β‐
unsaturated carboxylic acids
1 | INTRODUCTION
because of their wide‐ranging spectrum of biological
activities and broad applications in various fields of
Transition metal‐catalyzed oxidative cross‐coupling reac-
tions[1–5] are powerful tools for the formation of carbon–
carbon bonds to prepare complex and diverse aromatic
compounds, which remains a significant challenge in
organic synthesis. Such methods represent environmen-
tally benign and atom‐economical alternatives to
traditional coupling transformations,[5–10] which require
the use of two pre‐functionalized starting materials. Sev-
eral recent elegant and successful transformations[11–15]
have been developed for the preparation of aromatic
compounds via transition metal‐catalyzed oxidative
cross‐coupling. Among those transformations, Rh‐, Ru‐,
Cu‐ and Pd‐catalyzed direct oxidative cross‐coupling reac-
tions[16] have been extensively studied due to their high
efficiency. Although continuing efforts have been devoted
to develop efficient transformations for the synthesis of
aromatic compounds, oxidative coupling of aromatic com-
pounds is still highly favorable.
research. In addition, (E)‐1,2‐diarylethenes are also
considered as important building blocks in synthetic dyes
and molecules used in organic light‐emitting diodes and
liquid crystals.[17–20] Traditional syntheses of this sub-
structure, such as Wittig or Julia olefinations,[21,22]
Pd‐catalyzed Heck‐type coupling[23–27] and some reduc-
tion and condensation methods using suitable sub-
strates,[28–30] are waste‐intensive, limited in scope
and/or require multistep syntheses of starting materials.
Transition metal‐catalyzed alkenylation with aryl
(pseudo)halide arguably represents an efficient and
step‐economical strategy for the assembly of (E)‐1,2‐
diarylethenes. The selective synthesis of diarylalkenes
from widely available aryl (pseudo)halides by Heck‐type
reactions would be a welcome alternative.[31,32] However,
electronic and steric factors usually determine the
regiochemical outcome of the carbopalladation for simple
hydrocarbons, so that 1,1‐diarylalkenes are obtained from
styrenes.[33–35] As a result of the wealth of methods for
their preparation, cinnamic acids are alternative attractive
starting materials and more widely available in greater
structural diversity than styrenes. In Heck coupling reac-
tions with aryl (pseudo)halides, the carboxylate group
(E)‐1,2‐Diarylethene motif‐containing compounds are
prevalent in synthetic and natural products with a wide
spectrum of applications. (E)‐1,2‐Diarylethene scaffolds
have received a great deal of attention from biology and
synthetic chemistry researchers in the past decade
Appl Organometal Chem. 2019;e4914.
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ZHANG ET AL.
should direct the carbopalladation into its β‐position,
thereby leading to the intermediate formation of
diarylacrylic acids. Their in situ conversion into the desired
1,2‐diarylalkenes might be accomplished by an added
silver or copper decarboxylation catalyst. This catalyst
combination is known to effectively promote
decarboxylative cross‐coupling with formation of (E)‐1,2‐
diarylalkenes.[36–38]
under catalysis of PdBr2/CuF2 with (o‐biphenyl)PtBu2
at 170°C (Scheme 1, equation (3)). Wu et al.[36] then
reported the efficient decarboxylation of cinnamic acid
with aryl iodide catalyzed by
a combination of
palladium chloride and CyJohnPhos in the presence of
Ag2CO3 as an additive with good functional‐group
tolerance (Scheme 1, equation (4)). Recently, Djakovitch
et al.[42] described
a decarboxylative coupling of
Based on pioneering studies by Gooßen et al.,[39] tre-
mendous progress has been made in palladium‐
catalyzed decarboxylative cross‐coupling with cinnamic
acids. Pd(acac)2/CuI‐catalyzed decarboxylative coupling
of 1‐bromo‐4‐methylbenzene and cinnamic acid with
the assistance of PPh3 and phen at 160°C was achieved
in a yield of 91% (Scheme 1, equation (1)). Following
this significant lead, extensive efforts have been made
in the development of more active and selective transi-
tion metal catalytic systems. Goossen et al.[40] accom-
plished similar PdBr2/CuBr‐catalyzed decarboxylative
reaction under ligand‐free conditions at 170°C in a
79% yield (Scheme 1, equation (2)). In 2008, Gooßen's
group[41] reported the first decarboxylative coupling of
cinnamic acid with 1‐chloro‐4‐methylbenzene. A yield
of 82% of (E)‐1‐methyl‐4‐styrylbenzene was obtained
electron‐rich cinnamic acid with electron‐rich aryl
iodide to afford corresponding stilbenes and isomerized
biaryls (Scheme 1, equation (5)). Despite these indisput-
able advances, the catalysis was severely limited to
rather harsh reaction conditions (130–170°C). A notable
elegant exception was developed by Satoh and co‐
workers,[43] which indicated the potential of the replace-
ment of aryl halides with arylboronic acids. The
cinnamic acids possessing a hydroxyl group undergo
direct decarboxylative arylation under Pd(acac)2/
Cu(OAc)2 catalysis with LiOAc to form hydroxylated
stilbenes in 36–82% yields via oxidative Mizoroki–Heck
reaction (Scheme 1, equation (6)). There is still much
room for improvement, particularly in terms of substrate
scope and catalytic efficiency with new coupling
partners.
SCHEME 1 Pd‐catalyzed decarboxylative cross‐coupling of cinnamic acids with various coupling partners

ZHANG ET AL.
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TABLE 1 Decarboxylative coupling of cinnamic acids with phe-
nyl tosylates with various catalysts and co‐catalystsa
Oxygen‐based electrophiles have frequently been
employed as (pseudo)aryl halides in transition metal‐
catalyzed coupling reactions because they are easily pre-
pared from phenol derivatives, which are inexpensive
and readily accessible compared to aryl halides.[44–48]
The use of phenol derivatives instead of halides reduces
the production of halide waste, thus lowering the environ-
mental impact of the cross‐coupling process. Furthermore,
the use of phenol derivatives may exhibit orthogonal
reactivity to aryl halides. Among them, aryl tosylates are
inexpensive compared with the corresponding nonaflates
and triflates and are therefore desirable alternative precur-
sors for cross‐coupling reactions. Moreover, aryl tosylates
are easy to handle because of their high hydrolytic stability
and crystallinity.[49–52] Based on our efforts in transition
metal‐catalyzed cross‐coupling research and considering
our further interest in exploring the new‐type synthetic
methodology towards cross‐coupling,[53–57] herein we
report a successful attempt for the synthesis of stilbenes
using C–O electrophiles by decarboxylative coupling using
a combination of PdCl2(dppf) and CuCl2 in DMI
(1,3‐dimethylimidazolidinone) under mild conditions
(Scheme 1, equation (7)).
Entry
Catalyst
Co‐catalyst
Yield (%)b
1
Pd(OAc)2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
Cu(OAc)2
CuBr2
Cu(OTf)2
CuCl
60
57
36
65
77
71
80
89
14
21
85
78
81
8
2
PdCl2
3
PdI2
4
Pd(TFA)2
5
PdCl2(MeCN)2
PdCl2(PhCN)2
PdCl2(PPh3)3
PdCl2(dppf)
Pd(PPh3)4
Pd2(dba)3
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
PdCl2(dppf)
—
CuBr
18
15
—
—
—
—
Cu2O
PdI(OAc)2
Ag2CO3
—
2 | RESULTS AND DISCUSSION
CuCl2
We commenced our investigation with the substrates
cinnamic acid and phenyl tosylate in DMI using KOAc
as a base. To our delight, the desired decaboxylative cou-
pling product was formed in 60% yield by using Pd(OAc)2
as the catalyst and CuCl2 as the co‐catalyst (Table 1, entry
1). The screening of various commercially available palla-
dium salts, such as PdCl2, PdI2, Pd(TFA)2, PdCl2(MeCN)2,
PdCl2(PhCN)2, PdCl2 (PPh3)3 and PdCl2(dppf), revealed
that PdCl2(dppf) was the optimal catalyst and showed
the highest reactivity, giving the product (E)‐1,2‐
diphenylethene in 89% yield (Table 1, entries 2–8). Other
Pd(0)‐based catalysts were ineffective or less efficient for
this transformation. Other copper salts were also tested
in the reaction, and the effects were inferior to that of
CuCl2 (Table 1, entries 11–16). Some highly valent oxi-
dants, such as PhI(OAc)2 and K2S2O8, could not give the
desired product (Table 1, entries 17 and 18). A control
experiment showed that PdCl2(dppf) and CuCl2 were
essential for the amination reaction (Table 1, entries 19
and 20). Further optimization results for bases and sol-
vents are in the supporting information.
aReaction conditions: cinnamic acids (1.0 mmol), phenyl tosylates
(1.1 mmol), catalyst (5 mol%), co‐catalyst (20 mol%), KOAc (2.0 mmol),
DMI (2 ml), 100°C, 12 h.
bIsolated yields.
bearing both electron‐rich and electron‐poor groups on
the aromatic ring were well tolerated in this process,
resulting in the corresponding alkenylated products with
good to outstanding yields (Table 2, 2a–2g). The reaction
proceeded well with substrates bearing meta‐methoxy
substituents, thus giving the products in 94% yield
(Table 2, 2h). It is noteworthy that the reactions of 4‐
chlorocinnamic acid or 4‐bromocinnamic acid with phenyl
tosylate all efficiently proceeded to form the
decarboxylative products, with the halogen substituents
untouched during the reactions, which renders the cou-
pling products good candidates for further transformations
such as transition metal‐catalyzed functionalization of the
carbon–halogen bond (Table 2, 2i and 2j). Heteroaryl‐
substituted carboxylic acids led to a slightly lower yield of
the desired products (Table 2, 2k and 2l).
With the optimized reaction conditions in hand, we
then turned our attention to the investigation of substrate
scope. First, with phenyl tosylate as the substrate, we tested
the scope of the reaction with a representative set of deco-
rated cinnamic acids. As evident from Table 2, substrates
After achieving the alkenylation of various cinnamic
acids with phenyl tosylates, we further investigated the
direct reaction of various aryl tosylates under similar
reaction conditions (Tables 3–5). The reaction of
electron‐rich 4‐methoxycinnamic acid worked well with

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ZHANG ET AL.
TABLE 2 Scope of decarboxylative coupling with phenyl tosylates and various cinnamic acidsa,b
aReaction conditions: cinnamic acids (1.0 mmol), phenyl tosylates (1.1 mmol), PdCl2(dppf) (5 mol%), CuCl2 (20 mol%), KOAc
(2.0 mmol), DMI (2 ml), 100°C, 12 h.
bIsolated yields.
TABLE 3 Scope of decarboxylative coupling with various aryl tosylates and 4‐methoxycinnamic acidsa,b
aReaction conditions: 4‐methoxycinnamic acids (1.0 mmol), aryl tosylates (1.1 mmol), PdCl2(dppf) (5 mol%), CuCl2 (20 mol%),
KOAc (2.0 mmol), DMI (2 ml), 100°C, 12 h.
bIsolated yields.
TABLE 4 Scope of decarboxylative coupling with various aryl tosylates and 4‐chlorocinnamic acidsa,b
aReaction conditions: 4‐chlorocinnamic acids (1.0 mmol), aryl tosylates (1.1 mmol), PdCl2(dppf) (5 mol%), CuCl2 (20 mol%),
KOAc (2.0 mmol), DMI (2 ml), 100°C, 12 h.
bIsolated yields.

ZHANG ET AL.
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TABLE 5 Scope of decarboxylative coupling with various aryl tosylates and (E)‐hept‐2‐enoic acida,b
aReaction conditions: (E)‐hept‐2‐enoic acid (1.0 mmol), aryl tosylates (1.1 mmol), PdCl2(dppf) (5 mol%), CuCl2 (20 mol%), KOAc
(2.0 mmol), DMI (2 ml), 100°C, 12 h.
bIsolated yields.
a series of para‐substituted phenyl tosylates, proceeding
smoothly under the same reaction conditions as shown
above, thus affording the corresponding alkenylation
products in good yields (Table 3, 3b–3f). In general, the
substrates with electron‐donating groups on the aromatic
ring gave slightly higher yields. Interestingly, when
phenyl tosylate bears an bromo substituent, the (E)‐1‐
bromo‐4‐(4‐methoxystyryl)benzene compound could be
synthesized (Table 3, 3f), which suggests the mildness of
our protocol since, in previous transition metal‐catalyzed
protocols, the bromo substituent could not be tolerated.
The sterically hindered ortho‐substituted phenyl tosylate
also coped with this reaction condition, although with
lower yield (Table 3, 3g). For the substrate with thiazolyl,
the alkenylation product could be obtained in a yield of
77% (Table 3, 3h).
In addition to the 4‐methoxycinnamic acid derived
from 4‐methoxybenzaldehyde, the 4‐chlorocinnamic acid
derived from 4‐chlorobenzaldehyde is also a suitable
substrate (Table 4, 4a–4h). Diverse aryl tosylates with
electron‐withdrawing and electron‐donating groups can
undergo the reaction smoothly, with the corresponding
products isolated in modest to good yields (Table 4,
4b–4f). However, when a methyl group was installed
on the β‐carbon of cinnamic acid, corresponding prod-
uct was obtained and the yield dropped to 38%
(Table 4, 4g). Some heterocycles are also compatible
with our conditions, with (E)‐3‐(4‐chlorostyryl)pyridine
being produced in good yield (Table 4, 4h). No detection
of 1,1‐isomers was observed in all these cases.
As shown in Scheme 2, when cinnamic acid was replaced
by styrene, only a complicated reaction mixture of
unidentified products was obtained under optimum reac-
tion conditions (Scheme 2, equation (1)). When the reac-
tion was conducted with iodobenzene/bromobenzene/
phenylboronic acid, the formation of (E)‐1,2‐
diphenylethene was completely inhibited (Scheme 2,
equation (2)). This indicated that phenyl tosylate was
much more reactive than iodobenzene, bromobenzene
and phenylboronic acid under our reaction conditions.
(Cinnamoyloxy)copper, which was easily prepared using
CuCl2 and cinnamate acid, could react with phenyl tosyl-
ate smoothly without the addition of co‐catalyst (CuCl2),
indicating that (cinnamoyloxy)copper might be involved
in this catalytic cycle (Scheme 2, equation (3)). Then
(cinnamoyloxy)copper(I) was also prepared to investigate
the reaction with phenyl tosylate, and only 10% yield of
(E)‐1,2‐diphenylethene was obtained (Scheme 2, equation
(4)). Furthermore, when Cu(II) was replaced by Cu(I)
based on the standard conditions, we found the desired
yields decreased sharply, which indicated that the
transformation was more likely via a Cu(I)‐catalyzed path-
way (Table 1, entries 11–16). Moreover, when cinnamic
acid was replaced with potassium cinnamate, the
decarboxylative coupling with phenyl tosylate could afford
desired product in the absence of KOAc in a yield of 45%
(Scheme 2, equation (5)). Finally, the decarboxylative cou-
pling of both aryl tosylates and cinnamic acids was scalable
on the gram scale, which showed the potential of our
palladium‐catalyzed methods in industrial application
(Scheme 2, equation (6)).
Notably, in addition to cinnamic acids, aliphatic
α,β‐unsaturated carboxylic acids could also be converted
to the corresponding alkylvinylarenes in moderate yields
(Table 5, 5a–5c). Aliphatic tosylates such as benzyl
trifluoroborate and cyclopropyl tosylate were investi-
gated; however, no desired products were obtained. Fur-
thermore, no isomerization has been observed in these
transformations.
On the basis of our results and previous reports of cou-
pling reactions with aryl tosylates, we propose the reac-
tion mechanism shown in Scheme 3. α,β‐Unsaturated
carboxylic acids react with copper(II) species to give the
(E)‐3‐arylacrylate copper(II) complex
A
through
ligand‐exchange with the assistance of base, and then
(E)‐(arylvinyl)copper complex B is formed through
decarboxylation steps. The combination of PdCl2(dppf)
and KOAc generates the active [Pd(0)] catalyst which
We commenced the study with a series of control reac-
tions to identify the characteristics of this transformation.

6 of 8
ZHANG ET AL.
SCHEME 2 Control experiments and
scalability
SCHEME 3 Possible mechanism for
cross‐coupling
undergoes oxidative addition into the Ar&bond;OTs bond
to give the arylpalladium(II) complex C. Organocopper
complex B reacts with the arylpalladium complex C via
transmetallation to afford arylarylvinylpalladium (II)
complex D and regenerate copper(II) species. Finally the
desired coupled product is formed through reductive
elimination, and during the last step the active [Pd(0)]
species is regenerated to complete the catalytic cycle.
acids and aryl tosylates. Using simple and readily avail-
able metal reagents like PdCl2(dppf) as catalyst (5 mol%)
and CuCl2 as co‐catalyst (10 mol%), the successful con-
struction of new aryl–vinyl bond in the decarboxylative
process was achieved via the selective cleavage of
C&bond;C/C&bond;O bonds. We anticipate that this
cross‐coupling approach via a Pd/Cu‐catalyzed pathway
might offer access to several styrene compounds in the
synthesis of functionalized materials, complex molecules
and pharmaceuticals.
3 | CONCLUSIONS
We have developed an operationally simple and efficient
method of palladium/copper co‐catalyzed decarboxylative
coupling reactions towards the regioselective synthesis of
(E)‐1,2‐diarylethenes from α,β‐unsaturated carboxylic
ACKNOWLEDGEMENT
This work was Supported by the National Natural Science
Foundation of China (No. 21602189) and Program for

ZHANG ET AL.
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