Synthesis of Amides-Functionalized POPs-Supported Nano-Pd Catalysts for Phosphine Ligand-Free Heterogeneous Hydroaminocarbonylation of Alkynes

Article abstract of DOI:10.1002/adsc.202000242

Development of an approach for synthesis of efficient heterogeneous catalyst toward carbonylation reaction remains a challenge. Herein, we report our results of design and precise synthesis of amide-functionalized porous organic polymers (POPs) supported nano-Pd, and its applying in the first example of heterogeneous palladium-catalyzed hydroaminocarbonylation of alkynes under phosphine ligand-free conditions. A wide range of terminal alkynes and amines with various functional groups are smoothly converted into the corresponding branched α, β-unsaturated amides in moderate to good yields with high regioselectivity. The good catalytic performance of amides-functionalized POPs supported nano-Pd catalyst should be attributed to fine regulation of the catalytically active sites of the heterogeneous catalyst at the molecular level. The present study provided meaningful insights to design heterogeneous catalysts for phosphine ligand-free carbonylation reaction. (Figure presented.).

Full text of DOI:10.1002/adsc.202000242

Title: Synthesis of Amides-Functionalized POPs-Supported Nano-
Pd Catalysts for Phosphine Ligand-Free Heterogeneous
Hydroaminocarbonylation of Alkynes
Authors: Hongli Wang, Hangkong Yuan, Xinzhi Wang, Jian Zhao,
Dongcheng He, and Feng Shi
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000242
Link to VoR: https://doi.org/10.1002/adsc.202000242

Advanced Synthesis & Catalysis
10.1002/adsc.202000242
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Synthesis of Amides-Functionalized POPs-Supported Nano-Pd
Catalysts for Phosphine Ligand-Free Heterogeneous
Hydroaminocarbonylation of Alkynes
a,b
a
a,c
a
a
Hongli Wang, Hangkong Yuan, Xinzhi Wang, Jian Zhao, Dongcheng Wei, and
a,
Feng Shi *
a
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Centre for Green Chemistry and Catalysis, Lanzhou
Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, China
E-mail: fshi@licp.cas.cn
Dalian National Laboratory for Clean Energy, Dalian 116023, China
b
c
University of Chinese Academy of Sciences, No. 19A, Yuquanlu, Beijing, 100049, China
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. Development of an approach for synthesis of exclusively as catalyst for hydroaminocarbonylation
[
7]
efficient heterogeneous catalyst toward carbonylation of alkynes with ammonium,
primary [10a] nd
[8]
[9]
reaction remains a challenge. Herein, we report our results secondary, tertiary amines, and nitroarenes to
of design and precise synthesis of amide-functionalized produce α, β-unsaturated amides with high chemo- and
porous organic polymers (POPs) supported nano-Pd, and its regioselectivity (Scheme 1). It should be noted that the
applying in the first example of heterogeneous palladium-
catalyzed hydroaminocarbonylation of alkynes under
phosphine ligand-free conditions. A wide range of terminal
alkynes and amines with various functional groups are
smoothly converted into the corresponding branched α, β-
unsaturated amides in moderate to good yields with high
regioselectivity. The good catalytic performance of amides-
functionalized POPs supported nano-Pd catalyst should be
attributed to fine regulation of the catalytically active sites
of the heterogeneous catalyst at the molecular level. The
present study provided meaningful insights to design
heterogeneous catalysts for phosphine ligand-free
carbonylation reaction.
presence of phosphine ligand is necessary to promote
these Pd-catalyzed reactions. Furthermore, the use of
heterogeneous catalysts for hydroaminocarbonylation
is more desirable and attractive owing to the
convenience of recovering and recycling of the
[11]
catalysts. However, to the best of our knowledge, no
heterogeneous palladium catalyst system for
hydroaminocarbonylation reactions of alkynes has
been reported. Thus, it is highly desirable to develop a
heterogeneous
catalyst
for
efficient
hydroaminocarbonylation of alkynes under phosphine
ligand-free conditions.
Keywords: Hydroaminocarbonylation; Phosphine Ligand-
Free; Porous organic polymers; Surface functional groups;
Heterogeneous catalysis
Carbonylation reactions are prominent catalytic
approach to carbonyl compounds, such as aldehydes,
ketones, carboxylic acids, esters, and amides, which
[1]
are valuable intermediates in organic synthesis. So
far, more than 10 million tons of carbonyl compounds
annually have been produced through these reactions.
Scheme 1. Phosphine ligand-free heterogeneous palladium
catalyst system for hydroaminocarbonylation of terminal
alkynes with amines.
Among
the
carbonylation
reactions,
hydroaminocarbonylation of alkynes with amines is
one of the most atom economic and straightforward
approaches for the construction of α, β-unsaturated
amides,[ which are the key building blocks for
various materials ranging from polymers, flavors, and
2]
In heterogeneous catalysis, surface functional
groups play an important role in controlling and fine
tuning of the catalytic properties of heterogeneous
[3]
pharmaceuticals. Over the past decades, besides few
[4]
[5]
[12]
protocols rely on the use of rhodium, iron, and
stannum[ catalysts, palladium has been used almost
catalyst. In some way, the role of surface functional
6]
groups on heterogeneous catalyst is similar to organic
1
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Advanced Synthesis & Catalysis
10.1002/adsc.202000242
ligand in homogeneous catalysis. They could serve as
directing sites to anchor metal ions, which is beneficial
the homogeneous dispersion of metal ions. Moreover,
the catalytic performance of heterogeneous catalyst
could be finely regulated by changing the surface
functional groups around the active site. On the other
hand, amides are amongst the most frequently applied
coordinating directing groups in C-H functionalization
chemistry.[ Amides can direct a metal catalyst into
the proximity of a certain C-H bond in the molecule,
leading to its selective cleavage and subsequent
functionalization. If amide groups could be introduced
on their surface, it would finely regulate the catalytic
active sites of the heterogeneous catalyst at the
To study the structure-reactivity relationship, the
prepared amides-functionalized POPs supported nano-
Pd catalysts were characterized by TEM, XRD, XPS
and N adsorption-desorption analyses. First, the
2
morphology and size of Pd NPs in the amide-
functionalized POPs supported nano-Pd samples were
characterized by TEM (Figure S1). The TEM image of
the N-free sample, i.e., Pd/DVB, exhibited non-
uniform particle size distribution. Notably, the Pd
nanoparticles in phenyl and naphthyl amide-
functionalized POPs were homogeneously dispersed,
which might be attributed to the presence of phenyl
and naphthyl amide functional groups. The particle
size distribution of the Pd nanoparticles has been
shown in Figure S1. The mean particle diameter of Pd
nanoparticles is 5.3±1.4 nm and 10.2+2.3 nm with
particle size distribution from 3.0 to 8.0 nm and 6.0 to
18.0 nm in fresh and used Pd/DVB-0.2-PAM-Naph,
respectively (Figure S1n and 1r). In consideration of
the results with recycled Pd/DVB-0.2-PAM-Naph as
catalyst, the particle size of the Pd nanoparticles might
influence its catalytic performance less. The high-
angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM) images of
Pd/DVB-0.2-PAM-Naph clearly show the Pd species
uniformly dispersed in the DVB-0.2-PAM-Naph
13]
molecular
level.
Recently,
free-radical
polymerization[
14]
from the corresponding vinyl-
functionalized monomers has emerged as an effective
method for preparation of POPs, which are proved to
be a potential support in heterogeneous catalysis
owing to their remarkable properties, such as
hierarchical porosity, high surface area, high stability,
[15]
large pore volume, low skeleton density. Inspired
by the discussions above, we envisioned that POPs
containing amide groups could serve as promising
candidates of ligands and supports to construct the
efficient heterogeneous catalyst. In connection with
[16]
our interests in heterogeneous carbonylation, herein, support (Figure 2a). In addition, scanning electron
we describe the synthesis of amide-functionalized
POPs supported nano-Pd, and its applying in the first
example of heterogeneous palladium-catalyzed
hydroaminocarbonylation of alkynes under phosphine
ligand-free conditions (Scheme 1). The conditions
applied here are similar with homogeneous systems.
The amide-functionalized POPs supported nano-Pd
catalysts were prepared according to Figure 1. The
monomers of N-substituted acrylamides were
synthesized by the reaction of acryloyl chloride with
amines. The amide-functionalized POPs were
designed and synthesized via a free-radical co-
polymerizing N-substituted acrylamide monomers
with divinylbenzene monomer in different mole ratios
in THF at 100 ℃ for 24 h. After drying at 50 ℃ under
reduced pressure, amide-functionalized POPs was
obtained as white powder. This easy-to-get feature of
N-substituted acrylamide monomers made the amount
of porous polymers easily to scale-up. Following, the
amide-functionalized POPs supported nano-Pd
catalysts were prepared by a deposition-precipitation
method followed by reduction with hydrazine hydrate
solution.
microscopy-energy-dispersive X-ray spectroscopy
(SEM-EDS) map-ping images reveal the highly
dispersed character of all the functional elements (C,
N, O, and Pd, Figure 2b, c, d, and e).
Figure 2. (a) HAADF-STEM images of Pd/DVB-0.2-PAM-
Naph. (b-d) EDX elemental mapping images of C, N, O, and
Pd.
The XRD patterns of POPs supported nano-Pd
samples are shown in Figure S2. The POPs supported
nano-Pd catalysts show diffraction peaks at 40.1,
which can be ascribed to the diffraction peaks of
Pd(111). Compared with fresh Pd/DVB-0.2-PAM-
Naph, a new diffraction peak located at 26.6 °
indicating formation of the carbon (JCPDS card no:
7
5-2078) in Pd/DVB-0.2-PAM-Naph catalyst being
used for three times.
Figure 1. The Process for the Synthesis of Amides-
Functionalized POPs Supported Nano-Pd Catalysts.
Moreover, XPS studies of the catalysts were
performed to determine the chemical state of the Pd
nanoparticles. As shown in Figure S3, the XPS spectra
of POPs supported nano-Pd samples showed two
2
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Advanced Synthesis & Catalysis
10.1002/adsc.202000242
peaks at 336.0-336.2 and 341.2-341.4 eV that can be
attributed to Pd 3d5/2 and Pd 3d3/2 binding energies of
Pd(0). No peak of Pd 3d5/2 and Pd 3d3/2 was observable
in the reused Pd/DVB-0.2-PAM-Naph catalyst, which
might be attributed to the coverage of carbon on the
(entries 3-5). The yields of product 3a were slightly
increased when Pd/DVB-0.1-PAM-Bu and Pd/DVB-
0.1-PAM-Ph were used (entries 4-5). Compared with
aliphatic substituted amide, the yield of product was
higher when aromatic substituted amide was used, and
Pd/DVB-0.1-PAM-Naph exhibited better catalytic
performance, affording the desired product in 50%
yield (entry 5). Therefore, the influence of the amount
of PAM-Naph on the catalytic performance was
further investigated (entries 6-8), and it was
discovered that Pd/DVB-0.2-PAM-Naph and
catalyst surface. The N
Figure S4) showed that the BET surface areas of the
Pd/DVB, Pd/DVB-0.1-PAM, Pd/DVB-0.1-PAM-Bu,
Pd/DVB-0.1-PAM-Ph, Pd/DVB-0.1-PAM-Naph,
2
adsorption-desorption tests
(
Pd/DVB-0.05-PAM-Naph, Pd/DVB-0.2-PAM-Naph,
and Pd/DVB-0.3-PAM-Naph catalysts were in the
2
range of 311.8-941.1 m /g, and the BET surface area
Pd/DVB-0.3-PAM-Naph
showed
the
best
2
of Pd/DVB-0.2-PAM-Naph was the 570.7 m /g (Table
performance i.e., 65-66% yields (entries 7-8).
Furthermore, if the amount of Pd/DVB-0.2-PAM-
Naph was reduced to 20 mg, good result was still
obtained (entry 9). Notably, the catalyst is easily
recovered by simple filtration, and it can be reused
directly without further treatment. To our delight, 68%
S1). The results of elemental analysis (EA) showed
that the nitrogen content in catalysts varied from 0.36
to 2.17 wt% (Table S2).
Table 1. Reaction condition optimization for
rd
hydroaminocarbonylation of phenylacetylene with p-
NMR yield was maintained when it was used at the 3
a)
toluidine.
run (entry 11). Thus, the catalyst exhibits nice
reusability. It is clear that the catalytic performances
of nano-Pd are strongly dependent on the structures
and quantities of surface amides groups. We
concluded that the PAM-Naph group on the surface of
catalyst might play a critical role in highly dispersed
Pd NP formation, thus resulting in the nice catalytic
activity for the hydroaminocarbonylation reaction.
In order to test if the active species are leached
palladium from the Pd/DVB-0.2-PAM-Naph during
the reaction, hot filtration test was performed. After
being reacted for 1.5 h separate, the solid catalyst was
filtrated, and the remained mixture was further reacted
for another 10.5 h. It is found that the yield of desired
product was still 8% and the reaction stopped without
further progressing. Therefore, it is clear that the
Pd/DVB-0.2-PAM-Naph is the real catalyst and no
catalytically active palladium species is dissolved in
the solution. Moreover, the Hg poisoning experiment
was performed in order to provide further evidence of
the nature of the catalytic system (homogeneous vs.
heterogeneous). First, the reaction was performed for
3 h and 26% desired product was obtained determined
Number
Catalyst
Yieldb)
1
2
3
4
5
6
7
8
Pd/DVB
Pd/DVB-0.1-PAM
0
30
36
38
50
43
65
66
Pd/DVB-0.1-PAM-Bu
Pd/DVB-0.1-PAM-Ph
Pd/DVB-0.1-PAM-Naph
Pd/DVB-0.05-PAM-Naph
Pd/DVB-0.2-PAM-Naph
Pd/DVB-0.3-PAM-Naph
Pd/DVB-0.2-PAM-Naph
Pd/DVB-0.2-PAM-Naph
Pd/DVB-0.2-PAM-Naph
c)
d)
9
69 (78)
53
68
e)
1
1
0
1
f)
a)
Reaction conditions: phenylacetylene 1a (1.5 mmol), p-
toluidine 2a (1.0 mmol), catalyst (40 mg), NaI (2 mol%),
TsOH•H
2
O (2 mol%), CO (4.0 MPa), anisole (4.0 mL),
b)
1
1
20 ℃ , 18 h.
Determined by H NMR using
c)
1
triphenylmethane as internal standard material. Catalyst
by H NMR. Then, 147 mg Hg metal (280 equiv.) was
d)
(
3
20 mg). Isolated yield. The isolated yield of the product
a is higher than the NMR yield because that the actual
integral of C-H of alkene (=CH ) at 5.71 ppm is smaller than
added into the reaction mixture and allowed to react
for another 9 h and consequently, the final NMR yield
of desired product was determined to be 27%. Hg
poisoning experiment clearly proved that the
heterogeneous nature of amides-functionalized POPs
supported nano-Pd catalyst in this study.
2
e)
f)
theoretical value. Catalyst (10 mg). The catalyst (20 mg)
was recovered and reused for the 3 run.
rd
Next, the scope of amide-functionalized POPs
Then, the catalytic performance of various nano-Pd
catalysts was tested by the hydroaminocarbonylation
of phenylacetylene with p-toluidine as the model
reaction, and the results are summarized in Table 1.
The hydroaminocarbonylation reaction was initially
investigated with phenylacetylene with p-toluidine in
the presence of 40 mg catalyst under 4.0 MPa CO in
anisole at 120 ℃ for 18 h. No conversion was observed
if Pd/DVB was employed as catalyst (entry 1). When
Pd/DVB-0.1-PAM was employed, the desired product
was produced in 30% yield (entry 2). Then catalysts
containing different amide groups were evaluated
supported
nano
Pd-catalyzed
hydroaminocarbonylation reaction was investigated
(Table 2). It is worth mentioning that the reaction is
highly selective and only branched product was
observed in all cases. In general, both electron-
donating and -withdrawing substituents on the
benzene ring of aromatic amines were well tolerated.
With electron-rich methyl-, tert-butyl-, methoxy-, and
cycloalkyl-substituted anilines as starting materials,
moderate to good yields (3a-3f, 73-85%) were
achieved. Electron-deficient anilines bearing fluoro,
and chloro groups also proceeded well, affording their
3
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Advanced Synthesis & Catalysis
10.1002/adsc.202000242
corresponding products 3g-3h in 65% and 66% yields,
respectively. In addition, secondary amines also
underwent this hydroaminocarbonylation reaction
smoothly, giving the corresponding α, β-unsaturated
tertiary amides in 70-75% yields (3i-3j). No
conversion was observed when aliphatic amines, i.e.,
hexylamine and morpholine, were used as the
substrates, which might be attributed to the fact that
the key palladium hydride species can not be formed
bond afford the vinylpalladium intermediates C and C’.
Subsequent insertion of CO leads to the corresponding
acyl palladium species D or D’. Finally, the resultant
acylpalladium species D or D’ reacts with amines to
afford the desired product and regenerate the key
palladium-hydride species for the next catalytic cycle.
[17]
in the presence of the more basic aliphatic amines.
Next, reactions of p-toluidine with different alkynes
were examined. It should be noted that aromatic
alkynes bearing both electron-donating and -
withdrawing groups on the aromatic rings were all
smoothly converted to the corresponding α, β-
unsaturated secondary amides in moderate to good
yields (3k-3n, 70-81%). In addition to aromatic
alkynes, the aliphatic alkyne 1o was also compatible
with this reaction, affording the corresponding product
3
o in 64% yield. Due to the lower activity of aliphatic
alkyne, 5mol% NaI was added to improve the
[18]
efficiency of Pd-catalyzed carbonylations.
Table 2. Results of hydroaminocarbonylation of alkynes
a)
with amines.
Scheme 2. The proposed catalytic mechanism for
hydroaminocarbonylation of terminal alkynes with amines.
In conclusion, a series of amides-functionalized
POPs supported nano-Pd catalysts were synthesized
through
co-polymerization
of
N-substituted
acrylamide with divinylbenzene followed by
supporting Pd via deposition-precipitation method. By
applying the amide-functionalized POPs supported
nano-Pd catalyst, we have developed the first
heterogeneous Pd-catalyzed hydroaminocarbonylation
of terminal alkynes with amines under phosphine
ligand-free conditions. A variety of amines and
terminal alkynes with various functional groups were
smoothly transformed into the corresponding
branched α, β-unsaturated amides in moderate to good
yields with high regioselectivity. The good catalytic
performance could be attributed to the presence of
naphthyl-substituted acrylamide functional groups in
porous polymers. The work may provide new
perspectives for precisely regulating catalytic active
site of heterogeneous catalysts at the molecular level
and developing highly efficient non-phosphine
heterogeneous catalysts for carbonylation reaction.
a)
Reaction conditions: alkynes (1.5 mmol), amines (1.0
mmol), Pd/DVB-0.2-PAM-Naph (20 mg), NaI (2 mol%),
TsOH•H O (2 mol%), CO (4.0 MPa), anisole (4.0 mL),
2
1
20 ℃, 18 h. The isolated yield to the branched product was
b)
c)
e)
indicated. NaI (5 mol%), TsOH•H
2
O (5 mol%), 24 h.
O (5 mol%), 24 h. TsOH•H O (3 mol%), 24 h.
4 h. NaI (5 mol%), 24 h.
d)
TsOH•H
2
2
2
f)
Experimental Section
On the basis of the observed experimental results
and previous work,[
7, 8d, 8i, 10]
Synthesis of porous polymers with different N-
substituted amide: A series of porous polymers with
different N-substituted amide were prepared under the
solvothermal conditions via copolymerizing of N-
substituted acrylamide monomers with divinylbenzene
monomers in different mole ratios under solvothermal
conditions in an autoclave. As a typical run, 0.071 g (0.1
mmol) of acrylamide monomer and 1.170 g (0.9 mmol) of
a plausible mechanism of
this transformation was proposed (Scheme 2). Initially,
the Pd NPs undergoes oxidative addition with p-TsOH
to furnish the active palladium hydride species. Next,
coordination of the alkynes to the metal center
followed by insertion into the hydrogen-palladium
4
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Advanced Synthesis & Catalysis
10.1002/adsc.202000242
divinybenzene monomer were dissolved in 10 mL of THF
[
[
4] a) J. H. Park, S. Y. Kim, S. M. Kim, Y. K. Chung, Org.
Lett. 2007, 9, 2465-2468; b) Q. Huang, R. Hua, Adv.
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2
under an N atmosphere, followed by the addition of 32 mg
(
0.02 mmol) of azobisiso-butyronitrile (AIBN). After
stirring for 30 minutes, the mixture was then transferred into
an autoclave for the polymerization reaction to occur at
5] K. M. Driller, S. Prateeptongkum, R. Jackstell, M.
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1
00 °C for 24 h. After evaporation of THF at 65 °C under
vacuum, a white solid was obtained and denoted as DVB-
.1-PAM.
0
Typical procedure for preparation of am-ides-
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I. Ryu, Angew. Chem. 2005, 117, 1099-1102; Angew.
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functionalized POPs supported nano-Pd catalyst: DVB-
0
.1-PAM (0.5 g) was dispersed in deionized water (25 mL)
2 4
and K PdCl aqueous solution (1.0 mL, [Pd] 5.0 mg/mL)
was added into the solution under vigorous stirring. After
stirring 3 h, the pH value was adjusted to about 10 using 0.2
M NaOH and the solution was stirred for another 3 h at room
temperature. Then 1.0 mL of hydrazine in 3.0 mL of
deionized water was added to the solution and stirred for 4
h. The solid sample was recovered by centrifugation and
washed with water. The obtained solid was dried at 80 ℃
for 12 h. A gray solid sample was obtained and denoted as
Pd/DVB-0.1-PAM.
[
7] a) X. Ji, B. Gao, X. Zhou, Z. Liu, H. Huang, J. Org.
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Typical procedure for hydroaminocarbonylation of
alkynes with amines: a mixture of phenylacetylene (1.5
mmol), amine (1.0 mmol), Pd/DVB-0.2-PAM-Naph (20
Ghanam, J. Mol. Catal. A: Chem. 2002, 187, 17-33; d)
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2
mg), NaI (2 mol%), TsOH•H O (2 mol%) and anisole (4
31; e) U. Matteoli, A. Scrivanti, V. Beghetto, J. Mol.
mL) were added a glass tube which was placed in an 100
mL autoclave. After sealing and purging with CO for 3
times, the pressure of CO was adjusted to 4.0 MPa. Then the
reaction mixture was stirred at 120 ℃ for 18 h. After the
reaction finished, the autoclave was cooled to room
temperature and the pressure was carefully released.
4
6; h) J. Liu, H. Li, R. Duhren, J. Liu, A. Spannenberg,
Subsequently, Ph
3
CH was added to mixture for quantitative
R. Franke, R. Jackstell, M. Beller, Angew. Chem. 2017,
129, 12138-12142; Angew. Chem. Int. Ed. 2017, 56,
1
2
1
analysis by H NMR. The crude reaction mixture was
filtered and filtrate was concentrated by rotary evaporator
and purified by column chromatography on a silica gel
column (petroleum ether/ethyl acetate = 100/1-10/1) to give
the desired product 3a.
1976-11980; i) F. Sha, H. Alper, ACS Catal. 2017, 7,
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, 1334-1337.
9
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Financial supports from the NSFC (21633013, 21802147), the Co-
operation Foundation of Dalian National Laboratory for Clean
Energy of CAS (DNL201901), the Youth Innovation Promotion
Association (2019409), the ‘Light of West China’ Program, Fujian
Innovation Academy and Key Research Program of Frontier
Sciences of CAS (QYZDJ-SSW-SLH051), are gratefully
acknowledged.
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