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Copper immobilized at a covalent organic

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Cite this: Green Chem., 2018, 20,

framework: an efficient and recyclable
4891 heterogeneous catalyst for the Chan–Lam
coupling reaction of aryl boronic acids and
amines†
Yi Han, Mo Zhang, Ya-Qing Zhang and Zhan-Hui Zhang *

A polyimide covalent organic framework (PI-COF) with high thermal and chemical stabilities has been
readily prepared from commercially available and inexpensive reagents and was employed as an effective
support for heterogeneous copper. It was demonstrated that the obtained Cu@PI-COF is a highly active
Received 17th August 2018, heterogeneous catalyst which can effectively promote the Chan–Lam coupling reaction of aryl boronic
Accepted 2nd October 2018
acids and amines in an open flask without the aid of any base or additive. In addition, the catalyst could be
DOI: 10.1039/c8gc02611d readily recovered from the reaction mixture by simple filtration and reused for at least eight cycles without
rsc.li/greenchem any observable change in structure and catalytic activity.

Introduction media.30 Sawant and coworkers successfully applied the Cu–

Mn bimetallic catalyst to the above coupling reactions.31
The construction of the carbon–nitrogen bond is of particular Nasrollahzadeh and co-workers described that Fe@Pd nano-
importance in organic synthesis, medical chemistry, materials wires exhibited good activities for N-arylated amine synthesis
science and agricultural science. Therefore, various methods from arylboronic acids and amines.32 Recently, the Kobayashi
for efficiently forming C–N bonds have been extensively group developed a photoredox Chan–Lam procedure through
studied.1 Among all the available methods, the oxidative coup- the combination of copper and photoredox catalysis, and
ling of amines with arylboronic acids by copper salts reported expanded the substrate scope to include electron-deficient aryl
by Chan2 and Lam3 in 1998 is one of the most powerful and boronic acids under blue LED irradiation.33 A few hetero-
widely used synthetic methods for the efficient formation of geneous catalytic systems have been described, including the
C–N bonds. After this report, many modifications have been use of Cu-doped CoFe2O4 nanoparticles,34 Cu nanoparticles
made for this Chan–Lam coupling reaction to improve the immobilized over the Fe3O4–TiO2-L-dopa support,35 molecular
process efficiency by using different copper compounds such sieve immobilized copper,36 polymer supported Cu(II),37 the
as Cu(OAc)2,4–11 CuCl,12,13 CuO,14,15 Cu2O,16 Cu2S,17 and copper terephthalate metal–organic framework (MOF),38 nano-
copper-exchanged fluorapatite (Cu-FAP).18 A number of modifi- porous Cu2(BDC)2(BPY)–MOF,39 Cu/graphene,40 copper(I)-
cations have been made to improve the yield and efficiency of exchanged zeolites,41 and chitosan anchored Cu(II) schiff base
the Chan–Lam reaction using different copper salts in the complexes.42 Despite these indisputable advances, the
presence of various ligands.19–26 Besides these, there are reported methods still suffered from drawbacks such as the
several reports on this transformation using nickel-based cata- use of expensive ligands, toxic organic solvents and a large
lysts such as NiCl2·6H2O27 and Ni(OAc)2.28,29 Veisi and co- amount of base, high catalyst dosages, low yields, high reac-
workers reported that L-arginine/PdCl2 was also used as the tion temperatures, long reaction times, harsh reaction con-
catalyst for the Chan–Lam coupling reaction in aqueous ditions, tedious work-ups, and the formation of side products.
Therefore, the development of a new, more efficient, cheap
and easy to recycle catalyst system for the Chan–Lam coupling
National Demonstration Center for Experimental Chemistry Education, reaction is a particularly hot issue.
Key Laboratory of Inorganic Nanomaterials of Hebei Province, College of Chemistry In recent decades, covalent organic frameworks (COFs),
and Material Science, Hebei Normal University, Shijiazhuang, 050024, China.
which were constructed by the covalent linkage of organic
E-mail: [email protected], [email protected]
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ building blocks into predetermined network structures with
c8gc02611d low density, excellent crystallinity, large specific surface area,

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structural diversity, tunable compositions, high thermal stabi-

lity and designability, have emerged as a new structurally and
compositionally varied class of crystalline porous materials
and become one of the fastest growing fields in materials
science and chemistry.43 COFs have shown great potential
applications in gas adsorption,44 drug delivery,45 semi-
conductors,46 energy storage,47 separations,48 and proton con-
duction49 and catalysis.50 Since COF materials may be more
stable to water, organic solvents and even strong acidic or
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basic media, these characteristics can give COFs more advan-

tages, making them an ideal support for immobilizing active
catalytic species for catalysis, especially those catalytic reac-
tions that are carried out under relatively stringent conditions.
A few COFs have been used as supports to develop hetero-
geneous catalysts for a variety of chemical reactions such as
Suzuki–Miyaura coupling,51 Heck–Sonogashira coupling,52
reduction of nitroarenes,53 one-pot tandem reactions,54 and
asymmetric reactions.55
Recently, polyimide covalent organic frameworks (PI-COFs)
with high thermal stability, outstanding mechanical strength,
large pore sizes and superior chemical resistance were
designed and synthesized by combining tetrahedral and linear
building units via the imidization reaction. Even though Scheme 1 The preparation process of the Cu@PI-COF catalyst and the
catalytic Chan–Lam coupling reaction of aryl boronic acids and amines.
numerous studies have been done on the application of
PI-COFs as very promising functional materials in drug deliv-
ery,56 chemical and biological chemosensors,57 and the
removal of organic dye pollutants,58 the research on PI-COFs The synthesized Cu@PI-COF catalyst was characterized by a
as transition metal supports has been scarcely reported. As to variety of analytical techniques including Fourier transform
the great demand for a recyclable catalytic system,59 and in infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning
continuing our efforts on novel catalytic methodologies in electron microscopy (SEM), transmission electron microscopy
organic transformations,60 in this work, we report the first (TEM), and thermogravimetric (TGA) analysis.
example of a PI-supported Cu catalyst and its catalytic per- Fig. 1 shows the FTIR spectra of PMDA, MA, PI-COF and
formance for the Chan–Lam coupling reaction of aryl boronic Cu@PI-COF. The FTIR spectra of the PI-COF indicated the dis-
acids and amines (Scheme 1). In accord with our expectations, appearance of the band at 1850 cm−1 corresponding to the
the PI-immobilized Cu catalyst showed homogeneous-like cata- starting anhydride monomers and the intensity reduction of
lytic performance, and the optimal PI-supported catalyst the bands at 1640 cm−1 and 3300 cm−1 ascribed to the term-
(Cu@PI-COF) could be effectively recycled and reused. inal amino groups of the starting MA monomer. The four
bands at 1772, 1725, 1376 and 725 cm−1 corresponding to the
characteristic absorption of the polyimide were observed, indi-
cating that the product was completely imidized to form a
Results and discussion polyimide. Notably, the FTIR spectra of Cu@PI-COF did not
The route to prepare Cu@PI-COF is shown in Scheme 1. In the
experiments, pyromellitic dianhydride (PMDA) and melamine
(MA) with an equal molar ratio were mixed and ground. Then
the mixture was transferred into an alumina crucible and
heated to 325 °C for 4 h. After cooling down to room tempera-
ture in air, the resultant product was washed with water to
remove the unreacted starting precursors and finally dried to
obtain PI-COF in high yield. This synthetic process is rather
simple, cost-effective and environmentally-friendly because it
is solvent-free and does not produce any hazardous waste.
Subsequently, copper embedded Cu@PI-COF was simply pre-
pared by impregnating PI-COF in a solution of Cu(OAc)2 of
EtOH at room temperature. The total uploaded Cu amount, as
determined by inductively coupled plasma mass spectrometry
(ICP-MS) analysis, is up to 5.33 wt%. Fig. 1 IR spectra of PMDA, MA, PI-COF and Cu@PI-COF.

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Fig. 2 XRD images of Cu(OAc)2, PI-COF and Cu@PI-COF.

show any apparent change in PI, which indicated that the pres-
ence of Cu(OAc)2 did not affect the structure of PI.
The XRD characterization of PI-COF exhibited some rela-
tively strong diffraction peaks at 2θ = 18.9 and 29.6°, indicating
that the crystallinities of the materials were acceptable (Fig. 2).
The well maintained XRD patterns of Cu@PI-COF with
additional peaks at 12.8° (2θ) and 15.2° (2θ) compared to
PI-COF demonstrated the successful loading of Cu with reten-
tion of the COF integrity and minimal loss of crystallinity.61
The morphologies of PI-COF and Cu@PI-COF were investi-
gated by SEM and TEM (Fig. 3). The PI-COF and Cu@PI-COF Fig. 3 SEM images of PI-COF (a), Cu@PI-COF (b), and the recovered
materials displayed good crystallinity and a regular structure. Cu@PI-COF (c) and TEM images of PI-COF (d), Cu@PI-COF (e), and the
The SEM images indicated that PI-COF and Cu@PI-COF have a recovered Cu@PI-COF (f ).
spherical flower-like morphology with an average size of
50 nm. After the incorporation of Cu, the flowerlike mor-
phology of the original PI-COF in the Cu@PI-COF was
maintained.
The stability of the catalyst is an important parameter for
its practical applications. The thermogravimetric analysis
(TGA) displayed excellent thermal stability of PI-COF and
Cu@PI-COF with thermal decomposition temperatures exceed-
ing 297 and 401 °C, respectively (Fig. 4).
To investigate the chemical stability of Cu@PI-COF, we dis-
persed the samples in different organic solvents such as
MeOH, EtOH, CH3CN, DMSO, DMF, CH2Cl2, THF and toluene
for two days at room temperature. The sample was then col-
lected by filtration, washed with methanol and dried under
vacuum. To our delight, all samples also showed strong peaks
in the XRD pattern and had similar backbone connections in Fig. 4 TGA profiles of PI-COF and Cu@PI-COF.
the FT-IR profile. Therefore, the experimental results clearly
show that Cu@PI-COF has excellent thermal and chemical
stabilities. mixture was stirred for 12 h in ethyl acetate or ethyl lactate
Cu@PI-COF offers a high crystallinity and an exceptional (EL) in the presence of 20 mg Cu@PI-COF at ambient
stability, and it can serve as a heterogeneous catalyst for temperature in the absence of any bases (Table 1, entries 1
organic transformations. In order to validate our hypothesis, and 2). Gratifyingly, the reaction indeed occurred in THF,
we conducted the Chan–Lam coupling reaction of aryl water, toluene, acetonitrile or dichloromethane, giving the
boronic acids and amines using this catalyst. Initially, phenyl- desired product 3n in 31%, 41%, 43%, 51% and 56% yields,
boronic acid and aniline were selected as model substrates to respectively. The yield of 3n was improved when the reaction
optimize reaction conditions. As demonstrated in Table 1, was performed in EtOH, MeOH, DMSO, or DMF. A further
almost no target product was detected when the reaction study found that the MeOH/H2O solvent system was better for

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Table 1 Optimization of reaction conditions for the coupling reaction no substantial improvement in the yield, whereas the reaction
of phenylboronic acid and anilinea took a longer time and was not completed by decreasing the
amount of catalyst to 10 mg. In addition, in order to show-

Table 2 Substrate scope for the Cu/PI-COF catalyzed Chan–Lam

b coupling reaction of phenylboronic acids and aniline derivatives
Amount of Time Yield
Entry catalyst (mg) Solvent (h) (%)
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1 20 CH3COOEt 12 Trace
2 20 EL 12 Trace
3 20 THF 12 31
4 20 H2O 8.0 41
5 20 Toluene 12 43
6 20 CH3CN 8.0 51
7 20 CH2Cl2 8.0 56 Time Yield
8 20 EtOH 8.0 82 Entry R1 R2 Product (h) (%) m.p.(°C)
9 20 MeOH 8.0 85
1 H 2-OMe 3a 8.0 81 36–37 (ref. 19)
10 20 DMSO 8.0 86
2 H 3-OMe 3b 8.0 90 73–74 (ref. 62)
11 20 DMF 8.0 88
3 H 4-OMe 3c 8.0 92 104–105 (ref. 19)
12 20 EtOH–H2O (1 : 1) 8.0 76
4 H 2,4-(OMe)2 3d 8.0 82 Oil63
13 20 MeOH–H2O (1 : 1) 8.0 91
5 H 2-OEt 3e 8.0 80 47–48(ref. 64)
14 20 MeOH–H2O (1 : 2) 8.0 81
6 H 4-OEt 3f 8.0 93 73–74(ref. 19)
15 20 MeOH–H2O (2 : 1) 8.0 86
7 H 3-Me 3g 8.0 87 31–32 (ref. 34)
16 0 MeOH–H2O (1 : 1) 24.0 NR
8 H 4-Me 3h 8.0 90 88–89 (ref. 20)
17 10 MeOH–H2O (1 : 1) 10.0 71
9 H 3,4-Me2 3i 8.0 92 136–137 (ref. 62)
18 15 MeOH–H2O (1 : 1) 8.0 86
10 H 2,5-Me2 3j 8.0 83 Oil65
19 25 MeOH–H2O (1 : 1) 8.0 91
11 H 2,4,6-Me3 3k 8.0 81 56–57 (ref. 63)
20c 20 MeOH–H2O (1 : 1) 8.0 92
12 H 2-Et 3l 8.0 81 Oil4
a
Reaction conditions: Phenylboronic acid (1.25 mmol), aniline 13 H 4-CMe3 3m 8.0 90 66–67 (ref. 19)
(1 mmol), solvent (2 ml), room temperature. b Isolated yield based on 14 H H 3n 8.0 91 53–54 (ref. 19)
the amount of aniline. c The reaction was carried out on a 20 mmol 15 H 2-F 3o 12 73 60–61 (ref. 35)
scale in aniline. 16 H 4-F 3p 10 83 35–36 (ref. 19)
17 H 3-Cl 3q 8.0 87 112–113 (ref. 20)
18 H 4-Cl 3r 8.0 91 73–74 (ref. 20)
19 H 3-Cl-4-Me 3s 8.0 92 74–75 (ref. 66)
20 H 3-Cl-4-F 3t 10.0 85 Oil31
enhancing the yield of the corresponding product. Its ratio of 21 H 3,4-Cl2 3u 8.0 84 150–151 (ref. 67)
1 : 1 was found to be suitable for this transformation, giving 22 H 2,4,5-Cl3 3v 8.0 89 43–44 (ref. 69)
the expected product in 91% yield (Table 1, entry 13). The 23 H 2-Br 3w 8.0 81 48–49 (ref. 67)
24 H 3-Br 3x 8.0 88 Oil (ref. 68)
effect of catalyst loading was also tested by varying the 25 H 4-Br 3y 8.0 90 88–89 (ref. 19)
loading amount. It is noteworthy that no conversion took 26 H 4-I 3z 8.0 92 103–104 (ref. 67)
place when the reaction was performed in the absence of the 27 H 3-CF3 3aa 12 76 61–62 (ref. 69)
28 H 4-COMe 3ab 8.0 83 118–119 (ref. 33)
catalyst (Table 1, entry 16). The results showed that 20 mg of 29 H 4-NO2 3ac 12 0 —
catalyst was the best choice for completing the reaction. 30 2-OMe H 3ad 8.0 76 36–37 (ref. 19)
Increasing the amount of catalyst to more than 25 mg showed 31 3-OMe H 3ae 8.0 87 73–74 (ref. 62)
32 3-Me H 3af 8.0 85 31–32 (ref. 34)
33 4-Me H 3ag 8.0 89 88–89 (ref. 20)
34 4-Et H 3ah 8.0 87 85–86 (ref. 15)
35 4-CMe3 H 3ai 8.0 90 66–67 (ref. 20)
36 4-F H 3aj 12 81 35–36 (ref. 33)
37 4-Cl H 3ak 8.0 90 73–74 (ref. 33)
38 4-Br H 3al 8.0 91 88–89 (ref. 33)
39 2-OMe 4-Me 3am 8.0 83 36–37 (ref. 27)
40 3-OMe 4-Me 3an 8.0 89 70–71 (ref. 70)
41 3-Me 4-Me 3ao 8.0 87 134–135 (ref. 71)
42 4-Me 4-OMe 3ap 8.0 91 178–179 (ref. 33)
43 4-Me 4-Me 3aq 8.0 87 79–80 (ref. 63)
44 4-Me 4-F 3ar 10 81 51–52 (ref. 71)
45 4-Me 4-Cl 3as 8.0 92 83–84 (ref. 33)
46 4-Me 4-Br 3at 8.0 91 101–102 (ref. 71)
47 4-Et 4-Me 3au 8.0 90 85–86
48 4-CMe3 4-Me 3av 8.0 89 Oil2
49 4-Br 4-OMe 3aw 8.0 92 88–89 (ref. 68)
50 4-Br 4-Me 3ax 10.0 87 99–100 (ref. 68)
51 4-Br 4-F 3ay 10.0 84 49–50 (ref. 68)
52 4-Br 4-Cl 3az 8.0 93 91–92 (ref. 33)
53 4-Br 4-Br 3ba 8.0 92 107–108 (ref. 68)
Fig. 5 The recyclability of the catalyst. 54 4-BiPh 4-Me 3bb 8.0 86 133–134 (ref. 71)

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Table 3 Substrate scope for the Cu/PI-COF catalyzed Chan–Lam coupling reaction of aryl boronic acids and various amines

Entry Boronic acids Amines Product Time (h) Yield (%) m.p.(°C)
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1 C6H5 8.0 86 Oil (ref. 72)

2 C6H5 8.0 85 18–19 (ref. 69)

3 C6H5 8.0 83 Oil73

4 C6H5 8.0 90 46–47 (ref. 72)

5 C6H5 8.0 86 111–112 (ref. 72)

6 C6H5 12.0 83 160–161 (ref. 74)

7 C6H5 8.0 90 Oil15

8 C6H5 8.0 79 125–126 (ref. 75)

9 C6H5 12.0 53 164–165 (ref. 37)

10 2-OMeC6H4 24.0 67 Oil

11 3-MeC6H4 12.0 79 Oil

12 4-MeC6H4 10.0 85 114–115 (ref. 76)

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Table 3 (Contd.)

Entry Boronic acids Amines Product Time (h) Yield (%) m.p.(°C)
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13 4-EtC6H4 10.0 83 Oil

14 4-CMe3C6H4 10.0 82 Oil

15 Ph 8.0 87 89–90 (ref. 76)

16 4-ClC6H4 10.0 83 Oil

17 4-BrC6H4 10.0 81 133–134 (ref. 76)

18 4-MeC6H4 8.0 84 49–50 (ref. 17)

19 4-CMe3C6H4 8.0 82 90–91 (ref. 77)

20 Ph 8.0 87 14–15 (ref. 19)

21 4-FC6H4 8.0 92 Oil (ref. 34)

22 4-ClC6H4 8.0 90 90–91 (ref. 36)

23 4-BrC6H4 8.0 89 119–120 (ref. 34)

24 PhNH2 12.0 77 175–176 (ref. 19)

case the practical applicability of this developed method, we 8 hours. As expected, an excellent yield (92%) was obtained in
also investigated the possibility of using phenylboronic acid the amplified reaction (entry 20).
(25 mmol) and aniline (20 mmol) as substrates for scale syn- In addition to the catalytic activity, the recyclability of the
thesis in 40 mL of methanol/H2O at room temperature for catalyst is the most critical advantage in the practical appli-

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cation of heterogeneous reactions. The catalyst was easy to sep- conversion to give the desired N1-selective arylated products
arate from the reaction mixture by filtration. The recovered 6j–6p in high yields. Furthermore, the coupling reaction of 1H-
catalyst was washed with methanol, then dried and reused for imidazole with various boronic acids bearing both electron-
subsequent reactions without further purification. The catalyst donating and electron-withdrawing groups proceeded well
was recycled and reused eight times without any significant with a high yield of the expected products 6q–6w. A further
loss in its catalytic activity and original structure for the model evaluation of the scope of this methodology revealed that the
reaction (Fig. 5). This is mainly due to the excellent stability of reaction also proceeded smoothly with heteroaromatic boronic
Cu@PI-COF. In addition, we separated Cu@PI-COF from the acids such as 4-pyridylboronic acid to provide the corres-
reaction mixture at a conversion of 65% and the solution was ponding product 6x in 77% yield although the coupling reac-
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again stirred for 1 h. The reaction solution showed no further tion requires a long reaction time. Obviously, this protocol
reactivity, which clearly indicated the heterogeneous character- with a broad substrate applicability afforded a general and
istics of the Cu@PI-COF catalyst. The inductively coupled practical method for the construction of N-arylated products
plasma mass spectrometry (ICP-MS) analysis showed that the from N-containing heterocycles by the Chan–Lam reaction
amount of Cu leaching into the reaction mixture is very low using arylboronic acids as an aryl source.
(0.5 ppm). The SEM and TEM images of the fresh and recov-
ered catalysts indicated that little morphological changes
occurred (Fig. 3). Conclusions
Having identified the optimal reaction conditions, the
scope and limitations of the Cu@PI-COF catalysed aerobic In summary, copper supported on a COF was successfully pre-
coupling reaction between substituted anilines and phenyl- pared and employed as an efficient catalyst for the synthesis of
boronic acid were further explored and the experimental data N-arylated products by the Chan–Lam coupling reaction of
are given in Table 2. Generally, these reactions proceeded arylboronic acids with various amines in MeOH–H2O at room
smoothly, leading to the formation of N,N-diaryl amines in temperature under air without the aid of any base or additive.
high to excellent yields. Anilines bearing an electron-donating New heterogeneous copper catalysts can be readily prepared
group showed a slightly better result than those with an elec- from commercially available and inexpensive reagents.
tron-withdrawing substituent. ortho-Substituted anilines Moreover, the process provides the competitiveness of the
reacted well under our reaction conditions, even though recyclability of the catalyst without any loss of catalytic activity,
slightly lower yields were obtained. However, no product for- and the catalyst can be easily recovered and reused for at least
mation was observed for the reaction of aniline bearing the 8 cycles, thus making the process more environmentally
strong electron withdrawing –NO2 group with phenylboronic acceptable.
acid even after a long time (Table 2, entry 29). We then investi-
gated the reactivity of different phenylboronic acids.
Pleasingly, a variety of arylboronic acids bearing electron- Experimental
neutral, -donating, and -withdrawing groups underwent clean
General
conversion under these optimized conditions and furnished
the desired N,N-diaryl amines in good to excellent yields. Both All solvents and chemicals were obtained commercially and
bromo and chloro groups were well-tolerated under these con- were used without further purification. X-ray diffraction ana-
ditions and amenable for further functional group lysis was carried out using a PANalytical X’Pert Pro X-ray diffr-
transformation. actometer. The surface morphology and particle size were
To further exploit the potential of this method, different studied using a Hitachi S-4800 SEM instrument. Transmission
amines were examined with aryl boronic acids. As shown in electron microscopy (TEM) observation was performed using a
Table 3, aliphatic amines were also successfully transformed Hitachi H-7650 microscope at 80 kV. Melting points were
to the corresponding cross-coupling products in excellent con- determined on X-5 apparatus and were uncorrected. IR spectra
versions. Meanwhile, allylic amines were reactive and under- were obtained with KBr pellets in the range of 400–4000 cm−1
went the title reaction to afford expected products in high using a Thermo Fisher iS50 spectrometer. 1H NMR and 13C
yields. Additionally, heteroaromatic amines, such as pyridin-2- NMR spectra were recorded on a Bruker AV III-500 or Zhongke
amine, benzo[d]thiazol-2-amine and furan-2-ylmethanamine, Niujin AS 400 spectrometer using TMS as an internal standard.
were also efficiently transformed, affording the potentially bio- Mass spectra were recorded on a 3200 Qtrap instrument with
important N-arylated products in good yield (Table 3, entries an ESI source. ICP-MS analyses were carried out with an X
5–7). The reactions worked also well when 9H-fluoren-2-amine Series 2 spectrometer.
was used as a substrate (Table 3, entry 8). Benzamide could
also be transferred into the desired product 6i in good yield. Synthesis of PI-COF
Next, we focused our attention on the selective N-arylation MA and PMDA with equal molar ratios (10 mmol) were ground
of 1H-indazol-3-amine for the first time because it possesses in an agate mortar for 30 min, and the obtained mixture was
two different nucleophilic sites. It is interesting to observe that finally transferred into an alumina crucible with a cover and
all the electronically diverse boronic acids underwent clean heated to 325 °C for 4 h using a 5 °C min−1 heating rate. After

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cooling down to room temperature in air, the resultant 7 D. N. Rao, S. Rasheed, R. A. Vishwakarma and P. Das,
product was washed with water at 50 °C to remove the residual Chem. Commun., 2014, 50, 12911–12914.
MA precursors and finally dried at 80 °C overnight to obtain 8 A. S. Reddy, K. R. Reddy, D. N. Rao, C. K. Jaladanki,
PI-COF. P. V. Bharatam, P. Y. S. Lam and P. Das, Org. Biomol. Chem.,
2017, 15, 801–806.
Synthesis of Cu@ PI-COF 9 J. B. Lan, G. L. Zhang, X. Q. Yu, J. S. You, L. Chen, M. Yan
50 mg of the as-synthesised PI-COF was treated with 15 mg Cu and R. G. Xie, Synlett, 2004, 1095–1097.
(OAc)2 dissolved in 20 ml dry ethanol. The solution was stirred 10 T. D. Quach and R. A. Batey, Org. Lett., 2003, 5, 4397–4400.
11 D. N. Rao, S. Rasheed, S. Aravinda, R. A. Vishwakarma and
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for 4 h at room temperature, following which it was washed

with dry ethanol. Thus, the obtained Cu@PI-COF was then P. Das, RSC Adv., 2013, 3, 11472–11475.
activated using vacuum overnight at 80 °C. 12 S. Y. Moon, J. Nam, K. Rathwell and W. S. Kim, Org. Lett.,
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To a stirred solution of amine (1 mmol) in MeOH : H2O (1 : 1,
14 S. K. Das, P. Deka, M. Chetia, R. C. Deka, P. Bharali and
2 ml) were added aryl boronic acid (1.25 mmol) and
U. Bora, Catal. Lett., 2018, 148, 547–554.
Cu@PI-COF (20 mg) at room temperature. The reaction
15 R. K. Borah, P. K. Raul, A. Mahanta, A. Shchukarev,
mixture was stirred and the progress of the reaction was moni-
J. P. Mikkola and A. J. Thakur, Synlett, 2017, 28, 1177–1182.
tored by TLC. After completion of the reaction, the catalyst was
16 B. Sreedhar, G. T. Venkanna, K. B. S. Kumar and
separated by filtering and the mixture was diluted with H2O
V. Balasubrahmanyarn, Synthesis, 2008, 795–799.
and the product was extracted with EtOAc. The combined
17 K. Janikova, L. Jedinak, T. Volna and P. Cankar,
extracts were washed with brine and dried over Na2SO4. The
Tetrahedron, 2018, 74, 606–617.
crude product was purified using column chromatography
18 M. L. Kantam, G. T. Venkanna, C. Sridhar, B. Sreedhar and
over silica gel (eluent: ethyl acetate–hexane) to obtain the pure
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