Melamine-Based Porous Organic Polymers Supported Pd(II)-Catalyzed Addition of Arylboronic Acids to Aromatic Aldehydes

Article abstract of DOI:10.1007/s10562-020-03508-1

Abstract: A new type melamine-based porous organic polymers (SZU-1) has been synthesized with melamine and 2,2′-bipyridyl-5,5′-dialdehyde by a one-pot method and fully characterized. Divalent palladium salts were coordinated to this polymer network which successfully catalyzed the nucleophilic addition reaction of arylboronic acids to aromatic aldehydes. With only 1.0?mol% heterogeneous catalyst loading, high reaction yields (>?85%) can be achieved in most cases. The scope of substrates was also investigated and the catalyst showed universal applicability. Graphic Abstract: The loose and porous melamine-based porous organic polymers (SZU-1) are synthesized by melamine and 2,2′-bipyridyl-5,5′-dialdehyde. The performance of SZU-1 was characterized and most of the substrates achieved high yield (> 85%) in the catalytic performance test.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-020-03508-1

Catalysis Letters
https://doi.org/10.1007/s10562-020-03508-1
Melamine‑Based Porous Organic Polymers Supported Pd(II)‑Catalyzed
Addition of Arylboronic Acids to Aromatic Aldehydes
Kai Shen1 · Min Wen1 · Chaogang Fan1 · Shaohui Lin1 · Qinmin Pan1
Received: 13 September 2020 / Accepted: 19 December 2020
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC part of Springer Nature 2021
Abstract
A new type melamine-based porous organic polymers (SZU-1) has been synthesized with melamine and 2,2′-bipyridyl-
5,5′-dialdehyde by a one-pot method and fully characterized. Divalent palladium salts were coordinated to this polymer
network which successfully catalyzed the nucleophilic addition reaction of arylboronic acids to aromatic aldehydes. With
only 1.0 mol% heterogeneous catalyst loading, high reaction yields (> 85%) can be achieved in most cases. The scope of
substrates was also investigated and the catalyst showed universal applicability.
Graphic Abstract
The loose and porous melamine-based porous organic polymers (SZU-1) are synthesized by melamine and 2,2′-bipyridyl-
5,5′-dialdehyde. The performance of SZU-1 was characterized and most of the substrates achieved high yield (> 85%) in
the catalytic performance test.
Keywords Palladium catalysis · Heterogeneous catalysis · Porous organic polymers
1 Introduction
Supplementary Information The online version contains
Microporous materials have received great attention for their
supplementary material available at https://doi.org/10.1007/s1056
extremely high surface area and surface functional groups
diversities, and a great progress has been made in the past 2
2-020-03508-1.
Extended author information available on the last page of the article
Vol.:(0123456789)
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K. Shen et al.
decades [1–4]. Materials such as zeolite, silica, and activated
carbon (pore size < 2 nm) have been widely used as cata-
lysts and catalyst supports [5]. However, their applications in
heterogeneous catalysis still remain undeveloped [6–8]. The
covalently bonded porous organic polymers (POPs) have the
following advantages: (1) POPs have a high functional groups
diversity and can be coordinated with diferent catalysts [9]; (2)
compared with other homogeneous catalysts, POPs are insolu-
ble in any solvent, so the catalyst can be easily recycled [10]; (3)
their wettability can be easily adjusted, which is very benefcial
for improving mass transfer and catalyst performance [11]; (4) a
large number of nanopores can efectively enrich the reactants
and accelerate the reaction rate [12]. In summary, POPs-based
catalysts are much more recyclable compared to homogeneous
catalysts. In some reactions, even the same catalyst activity as
in homogeneous reactions can be achieved [13].
melamine and 1,4-phthalaldehyde were used as raw mate-
rials in a one-pot process. Melamine is a very simple and
readily available compound, and the method does not require
anhydrous and oxygen-free conditions, which is very suit-
able for large-scale synthesis. The authors tried a variety of
diferent monomers, confrming that this method is highly
selective, making the functionalization of target materials
possible. SNW-1 has a very high surface area (>1000 m2/g)
and excellent heat resistance (Tdec > 400 °C), which dem-
onstrated high potential as a catalyst supporting material.
In our research, 4,4′-biphenyldicarboxaldehyde was used
as the monomer and the bipyridine ligand can be easily
implanted into the POPs to efectively coordinate with pal-
ladium (Scheme 1). The produced POPs (SZU-1) is loose
and porous, which is an ideal support for heterogeneous
catalysts.
Over the past decade, our group has been working on
Pd(II)/2,2′-bipyridine-catalyzed nucleophilic addition reac-
tions. A series of diferent nucleophilic addition reactions,
including the addition of arylboronic acids to aromatic alde-
hydes [14], imines [15] and α, β-unsaturated carbonyl com-
pounds [16] have been developed, in which highly efcient
additions were achieved under mild conditions. Based on
our previous research, we want to further expand its applica-
tion on heterocatalysis. The addition reaction of arylboronic
acids to aromatic aldehydes will be tested under heterogene-
ous catalytic conditions to probe the reusability of the pre-
cious palladium catalysts. Though porous materials like zeo-
lites are currently widely used as heterogeneous supported
catalysts [17, 18], it is difcult to coordinate them with tran-
sition metals due to the limitation of its elemental structure
because most transition metals need to be coordinated with
organic ligands to achieve good catalytic activity [19–22].
So, the application of inorganic porous materials in diverse
organic functional groups transformations is greatly limited.
Therefore, heterogeneous catalytic materials that can
efectively coordinate with metals are highly expected. In
2009, Schwab et al. synthesized a nitrogen-rich polymer
network (SNW-1) [23] with a high surface area, in which
SZU-1 with bipyridine segments has been successfully
synthesized, and its 13C NMR spectrum and FT-IR were
proved to be consistent with the reported similar structure
in literature [23]. BET test showed that surface area is high
to 333 m2/g.
Initially, Pd(OAc)2 was selected as the catalyst to coor-
dinate with SZU-1, but only a trace amount of product is
given in the addition of arylboronic acids to aromatic alde-
hydes. Then the more active cationic Pd(II) becomes a better
choice. Under cationic Pd(II) conditions, good yields had
been achieved and functional group tolerance is perfect. At
the same time, the recycle test of the catalyst showed that the
yield can still be higher than 80% after 4 cycles.
2 Experiment
2.1 Catalyst Preparation
2.1.1 Preparation of SZU‑1 (bipyridine/biphenyl = 1:2)
Melamine (101 mg, 0.80 mmol), [2,2′-bipyridine]-
5,5′-dicarbaldehyde (86 mg, 0.40 mmol) and
Scheme 1 Synthesis of SZU-1
1 3

Melamine-Based Porous Organic Polymers Supported Pd(II)-Catalyzed Addition of Arylboronic…
[1,1′-biphenyl]-4,4′-dicarbaldehyde (168 mg, 0.80 mmol)
were mixed and completely dissolved in DMSO (5 mL)
at 100 °C. 2 mL of 3.0 M aqueous acetic acid was added.
All the mixture was loaded in a hydrothermal reactor and
sealed. The reaction was running at 135 °C for 72 h. Cooled
the reactor to room temperature and a gel-like product was
obtained. THF (15 mL) was added and stirred for 12 h, then
centrifuged at 10,000 rpm for 5 min to separate the solid
yellow powder, which was fnally vacuum dried at 120 °C
for 12 h. The yield was 83%.
difraction (XRD) was tested on X’Pert-Pro MPD (PAN-
alytical B.V., Netherlands). The Solid-state NMR spec-
trum was recorded by AVANCEIII/WB-400 AVANCEIII/
WB-400 Solid-state NMR spectrometer wide bore (Bruker
1
Corporation, Germany). H NMR spectra were recorded
on a BRUKER AVANCE III HD (400 MHz) spectrometer.
13C NMR spectra were recorded on a BBRUKER-OLD
AVANCEIII HD-400 (100 MHz) spectrometer with com-
plete proton decoupling. Fourier transform infrared (FT-
IR) spectra were collected from Nicolet 6700 spectrometer
(Nicolet Instrument Corp., US) with a wavenumber range
of 4000–400 cm−1.
2.1.2 Preparation of PdCl2@SZU‑1
40 mg of SZU-1 and 50 mg of PdCl2 were mixed in 10 mL
of CH3CN, refuxed for 12 h, fltered and dried under vac-
uum. The color of SZU-1 changed from light yellow to
orange after coordination. The coordination rate is 5.2 wt%
calculated by the mass change after ashing.
2.3 Catalyst Testing
PdCl2@SZU-1 (10 mg, 1.0 mol%) and AgNO3 (5 mg,
2.0 mol%) were mixed in CH3NO2 (2 mL), and stirred at
80 °C for 1 h, then 1 mmol arylboronic acid and 0.5 mmol
aromatic aldehyde added. The reaction was carried out for
24 h. During the reaction, an appropriate amount of arylbo-
ronic acid could be added. The reaction mixture was concen-
trated and the target product was purifed by column chro-
matography on silica gel to determine the catalyst efciency.
2.2 Catalyst Characterization
Brunauer–Emmett–Teller (BET) test is at TriStar II 3020
(Micromeritics., US), 120 °C degassing for 24 h. X-ray
Fig. 1 13C MAS NMR spectrum of SZU-1
1 3

K. Shen et al.
3 Results and Discussion
3.1 Catalyst Characterization
SZU-1 was frstly characterized by solid-state NMR spec-
trum and FT-IR (Fig. 1). The 13C MAS solid-state NMR
spectrum showed that two peaks at 166 ppm and 53 ppm can
be assigned as the carbons on the azine ring of melamine,
and -NH- in melamine is boned to –CH–, which is also con-
sistent with the literature [23]. As SZU-1 was composed of
biphenyl and bipyridyl segments, the two peaks at 148 ppm
and 144 ppm belong to the carbons at positions 3 and 4
of bipyridines. The peak of carbon atoms 6 showed up at
193 ppm. 134 ppm and 129 ppm correspond to two pairs of
aromatic carbons of biphenyl.
FT-IR spectroscopy (Fig. 2) showed the melamine-NH2
stretching vibration at 3400 cm−1, and the primary ammo-
nia deformation vibration at 1700 cm−1. 1550 cm−1 and
1480 cm−1 attribute to the quadrant and semicircle stretching
of the triazine rings [24]. This concluded that melamine had
been successfully incorporated into the network. In addition,
the stretching vibration peak (1600 cm−1) of the imine bond
was not observed on the FT-IR spectrum. It revealed that
the imines from the condensation of melamine and aldehyde
were subjected to a secondary addition.
Fig. 3 X-ray difraction (XRD) of PdCl2 (blue), Pd@SZU-1 (red),
SZU-1 (black)
3.2 Catalyst Performance Evaluation
Then the catalytic performance of SZU-1 was evaluated.
Initially, as shown in Table 1, Pd(OAc)2 was used as the pal-
ladium catalyst and reacted in 4 diferent solvents (Table 1,
Entries 1–4). However, only trace amount of product was
detected in nitromethane (Table 1, Entries 1). Therefore,
the more reactive cationic PdCl2/AgNO3 was chosen as
the palladium species. The vacant coordination sites of the
cationic palladium centers make it easier for the unsaturated
bonds to coordinate, which helps the following unsaturated
bonds insertion. As shown in Entries 5–7, the reaction takes
nitromethane as a solvent at 80 °C for 24 h (Table 1, Entry
7), and the starting materials are completely converted.
Nitromethane is a very good reaction solvent for its high
polarity and weak coordination ability [14]. The efect of
reaction time on the reaction results was also considered,
and it was found that the raw materials had almost com-
pletely been consumed in 24 h (Table 1, Entries 7–8). It was
concluded that the best results were under PdCl2/AgNO3
with nitromethane as the solvent, with a yield of 95%. In
addition, the catalytic activity was also tested for those
catalysts with diferent percentages of bipyridine segments
(Table 1, Entries 7, 9, 10). The result showed that the SZU-1
supported catalyst with 33%, 66%, and>99% bipyridine had
almost the same performance. Therefore, for economic con-
siderations, an SZU-1 with a bipyridyl percentage of 33%
was used as the optimal catalyst.
In addition, SZU-1, PdCl2 and Pd@SZU-1 were char-
acterized by X-ray difraction (Fig. 3). The result shown in
Fig. 3 revealed that PdCl2 has been coordinated on SZU-1.
The morphology of SZU-1 was tested by electron scan-
ning electron microscope (SEM) and it’s found that the
SZU-1 was loose and porous spherical particles (Fig. 4).
The BET test results gave a surface area as 330 m2/g and a
NLDFT micropore volume as 0.67 cm3/g (Fig. 5).
Then, the scope of the substrates was investigated. Sub-
strates are divided into two groups: p-nitrobenzaldehyde
was fxed as the reactant to react with diferent arylboronic
Fig. 2 FT-IR spectrum of SZU-1
1 3

Melamine-Based Porous Organic Polymers Supported Pd(II)-Catalyzed Addition of Arylboronic…
Fig. 4 Scanning electron micrograph (TEM) of SZU-1
Fig. 5 Nitrogen sorption isotherms and NLDFT pore size distribution of SZU-1 (triangle), Pd@ SZU-1 (circle)
acids in one group, and phenylboronic acid as the fxed reac-
concluded from Tables 1 and 2 that SZU-1 showed very high
tant to test aromatic aldehydes in another group. It can be
catalytic reactivity. The similar catalytic performance as the
1 3

K. Shen et al.
Table 1 Efect of phenylboronic acid addition to p-nitrobenzaldehyde
OH
B(OH)2
+
CHO
O2N
Pd(II)@SZU-1
NO2
2a
3aa
1a
Entry
Catalyst
Bipyridyl percentage (%)a Solvent
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
9
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2/2AgNO3
PdCl2/2AgNO3
PdCl2/2AgNO3
PdCl2/2AgNO3
PdCl2/2AgNO3
PdCl2/2AgNO3
>99
>99
>99
>99
>99
>99
>99
>99
33
CH3NO2
THF/H2O
Toluene/H2O
CH3OH
Dioxane
Toluene/H2O
CH3NO2
CH3NO2
CH3NO2
CH3NO2
24
24
24
24
24
24
24
12
24
24
Trace
0
0
0
34
52
95
61
91
94
10
66
Reaction conditions: PhB(OH)2 (1 mmol), 4-nitrobenzaldehyde (0.5 mmol), Pd@ SZU-1 (10 mg, 1 mol%), AgNO3 (5 mg, 2.0 mol%), solvent
(2 mL).
bipyridine
aBipyridyl percentage=
bipyridine+biphenyl
bIsolated yield
general homogeneous catalyst was achieved. Compared with
our previously research, the catalytic performance is compa-
rable to that of homogeneous reactions [14].
be more stable and difcult to be oxidized, but also pro-
moted the reaction yield to more than 95%. However, with
the decrease of electron-withdrawing properties, the yields
also showed a downward trend. For the aldehydes with halo-
gen substituents, the reaction yields decreased for 2d and
2e (Table 3, Entries 4, 5). When benzaldehyde 2f was sub-
jected in the reaction (Table 3, Entries 6), only a 55% yield
was given due to the less electrophilicity and its unstability
in the air. Finally, for 2g and 2h (Table 3, Entries 7, 8) with
electron-donating groups, the yields were greatly reduced.
Aromatic aldehydes with electron-donating groups are not
only difcult to be added but they are easily oxidized to car-
boxylic acids during the reaction, which made the reaction
yield dropped sharply.
Since this reaction is a nucleophilic addition, theoreti-
cally an electron-donating group on nucleophiles and an
electron-withdrawing group on electrophiles would favor
the reaction. Therefore, it’s observed in Table 2 that difer-
ent arylboronic acids all gave excellent results with > 90%
isolated yields, whether it is the strong electron-donating
groups 1b, 1c (Table 2, Entries 2, 3), the medium electron-
donating groups 1d, 1h (Table 2, Entries 4, 8) or the weaker
electron-withdrawing groups 1e, 1f (Table 2, Entries 5, 6).
As the arylboronic acid with an electron donating group can
be decomposed by protonolysis, it is necessary to add a cer-
tain more amount of arylboronic acid in a timely manner to
get a complete conversion. In addition, 1g (Table 2, Entry 7)
with a larger steric hindrance also gave a high yield. It can
be concluded that the POPs-supported catalysts have good
catalytic performance for diferent arylboronic acids.
As shown in Table 3, diferent aromatic aldehydes were
used as substrates. When the substituents on the benzene
ring changes from electron-withdrawing groups to electron-
donating groups, the yield changed drastically. For exam-
ple, strong electron-withdrawing groups of 2a, 2b, and
2c (Table 3, Entries 1, 2, 3) not only made the aldehydes
Finally, the catalytic cycle test was also carried out and
the results were shown in Fig. 6. The result revealed that
after 4 complete cycles, the reaction yield still reached more
than 80%, and for the frst three cycles the yields were more
than 90%. By the comparison of TEM images (Fig. 7), it is
clearly observed that a number of Pd(0) nanoparticles (dark
dots in Fig. 7b) were generated after 4 cycles. A very similar
phenomena were observed in literature [25]. The formation
of Pd(0) was supposed to be caused by the cross-coupling
of arylboronic acids, and the addition of arylboronic acids to
aldehydes is a divalent-Palladium catalysis in which Pd(0) is
1 3

Melamine-Based Porous Organic Polymers Supported Pd(II)-Catalyzed Addition of Arylboronic…
Table 2 Cationic Pd(II)@SZU-1 catalyzed addition of arylboronic acid to p-nitrobenzaldehyde
HO
Ar
CHO
ArB(OH)2
+
Pd(II)@SZU-1
NO2
NO2
2a
Entry
1
ArB(OH)2
B(OH)2
Product
Time (h)
24
Yield (%)a
95
1a
1b
1c
1d
1e
1f
3aa
3ba
3ca
3da
3ea
3fa
OH
O2N
O2N
O2N
O2N
O2N
O2N
O2N
2
3
4
5
6
7
24
24
24
24
24
48
81
89
95
94
88
71
OH
MeO
B(OH)2
OCH3
OH OCH3
B(OH)2
OMe
OH
B(OH)2
OH
F
B(OH)2
F
OH
OH
Cl
B(OH)2
B(OH)2
Cl
1g
3ga
8
1h
3ha
24
94
OH
B(OH)2
O2N
Reaction conditions: ArB(OH)2 (1 mmol), p-nitrobenzaldehyde (0.50 mmol), Pd(II)@SZU-1 (10 mg, 1 mol%), AgNO3 (5 mg,), CH3NO2
(2 mL), 80 °C.
aIsolated yield
1 3

K. Shen et al.
Table 3 Cationic Pd(II)@SZU-1 catalyzed addition of phenylboronic acid to aromatic aldehydes
B(OH)2
+
HO
Ar
ArCHO
Pd (II)@ SZU-1
1a
Entry
1
ArCHO
Product
Time (h)
24
Yield (%)a
95
2a
2b
2c
2d
2e
3aa
3ab
3ac
3ad
3ae
OH
O2N
CHO
NO2
2
3
4
5
18
18
24
24
96
95
60
85
OH
H3CO2S
CHO
SO2CH3
NO2
CHO
OH NO2
O2N
F
NO2
OH
OH
CHO
F
Cl
CHO
Cl
6
7
8
2f
3af
3ag
3ah
48
48
48
55
30
17
OH
OH
OH
CHO
2g
2h
CHO
H3CO
CHO
OCH3
Reaction conditions: PhB(OH)2 (1 mmol), ArCHO (0.50 mmol), Pd(II)@ SZU-1 (10 mg, 1 mol%), AgNO3 (5 mg), CH3NO2 (2 mL), 80 °C
aIsolated yield
1 3

Melamine-Based Porous Organic Polymers Supported Pd(II)-Catalyzed Addition of Arylboronic…
4 Conclusion
In our research, a nitrogen-rich porous organic polymers
(SZU-1) was synthesized and characterized. It has high
surface area (330 m2/g). Its loose and porous surface with
bipyridine segments is very suitable as supporting mate-
rial for heterogeneous palladium catalysis. Characteriza-
tion by FT-IR, XRD and 13C NMR confrmed that bipy-
ridine segments have been successfully incorporated and
palladium catalyst was coordinated. In terms of catalytic
performance, this heterogeneous catalyst achieved high
yields for the nucleophilic addition of arylboronic acids
to aldeydes under relatively mild conditions with low cata-
lyst loadings. The reaction showed excellent tolerance to
diferent arylboronic acids and aldehydes. Among 15 dif-
ferent substrates, 10 examples gave yields of over 80%,
indicating the excellent catalytic efciency and substrate
tolerance of this catalyst. Moreover, SZU-1 demonstrated
excellent chemical stability, and the yield can still exceed
80% after 4 catalytic cycles.
Fig. 6 SZU-1 catalytic cycle test
non-reactive [14]. It’s speculated the deactivation of Pd(II)
to Pd(0) caused the yield drops in recycling experiments.
Fig. 7 Transmission electron microscope (TEM) of without catalytic test (a) and after 4 catalytic cycles (b)
1 3

K. Shen et al.
14. Lin SH, Lu XY (2007) Cationic Pd (II)/bipyridine-catalyzed addi-
tion of arylboronic acids to arylaldehydes. One-pot synthesis of
unsymmetrical triarylmethanes. J Org Chem 72:9757–9760
15. Yang ZY, Ni YX, Liu R, Song KX, Lin SH, Pan QM (2017) In situ
generated cationic Pd (II)/bipyridine-catalyzed addition of arylbo-
ronic acids to N-sulfonyl-arylaldimines. J Org Chem 58:2034–2037
16. Ni YX, Song KX, Shen K, Yang ZY, Liu R, Lin SH, Pan QM
(2018) Cationic Pd (II)/bipyridine-catalyzed conjugate addition of
arylboronic acids to α, β-unsaturated carboxylic acids in aqueous
media. Tetrahedron Lett 59:1192–1195
Acknowledgements We gratefully acknowledge the National Natural
Science Foundation of China (Nos. 21104049, 21176163, 21576174),
Specialized Research Fund for the Doctoral Program (SRFDP) of
Higher Education (No. 20113201120006), the Priority Academic
Program Development (PAPD) of Jiangsu Higher Education Institu-
tions (Grant No. 2018), Soochow University Funds (Nos. 14109001,
Q410900510) and Suzhou Industrial Park Fund for fnancial support.
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Authors and Afliation
Kai Shen1 · Min Wen1 · Chaogang Fan1 · Shaohui Lin1 · Qinmin Pan1
* Shaohui Lin
linshaohui@suda.edu.cn
Green Polymer and Catalysis Technology Laboratory
(GAPCT), College of Chemistry, Chemical Engineering
and Materials Science, Soochow University, 199 Ren’ai
Road, Suzhou 215123, People’s Republic of China
* Qinmin Pan
qpan@suda.edu.cn
1
State and Local Joint Engineering Laboratory for Novel
Functional Polymeric Materials, Jiangsu Key Laboratory
of Advanced Functional Polymer Design and Application,
Key Laboratory of Organic Synthesis of Jiangsu Province,
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