Metalated Porous Phenanthroline-Based Polymers as Efficient Heterogeneous Catalysts for Regioselective C?H Activation of Heteroarenes

Article abstract of DOI:10.1002/asia.202100695

Direct C?H bond activation of heterocycles as a step-economical and environmentally friendly approach to build the heterobiaryls motifs is highly attractive, but it still has a challenge to design and prepare a cheap and regioselective heterogeneous catal

Full text of DOI:10.1002/asia.202100695

doi.org/10.1002/asia.202100695
Full Paper
Metalated Porous Phenanthroline-Based Polymers as Efficient
Heterogeneous Catalysts for Regioselective CÀ H Activation of
Heteroarenes
[
a]
[b]
[a]
[a]
[a]
Yongquan Tang, Zhifeng Dai, Sai Wang, Fang Chen, Xiangju Meng,* and
[
a, c]
Feng-Shou Xiao*
Abstract: Direct CÀ H bond activation of heterocycles as a
step-economical and environmentally friendly approach to
build the heterobiaryls motifs is highly attractive, but it still
has a challenge to design and prepare a cheap and
regioselective heterogeneous catalyst. To tackle this chal-
lenge, we have introduced Ni species into a porous
phenanthroline-based organic polymer donated as POP-
Phen@Ni. This heterogeneous catalyst shows excellent cata-
lytic performances in regioselective CÀ H activation of hetero-
cycles, even better than those of the corresponding homoge-
nous catalyst. H/D exchange experiments show that the
lithium bis(trimethylsilyl)amide (LiHMDS), a base added in the
reaction, play a very important role during the reaction
processes. We believe that this heterogeneous catalyst would
open a new door for design of heterogeneous catalysts to
efficiently catalyze the regioselective CÀ H activation of
heterocycles.
Introduction
Regioselective CÀ H arylation of heterocycles was firstly
[2a]
shown by Ohta in 1990 using Pd-based catalysts, and latter Ir-
[6,4a]
Heterobiaryl are valuable motifs in many natural products,
and Cu-based catalysts have been reported.
Notably, in
[1]
fragrances, agrochemicals, and pharmaceuticals. In the past
decades, highly effective transition-metal-catalyzed cross-cou-
pling reactions are powerful methods to construct the hetero-
these reported examples it is normally required a directing
group on the arenes which is capable of coordinating the metal
[7]
catalyst and then facilitating CÀ H activation. After the
reaction, the directing group has to be removed, which is not
atom-economy. To overcome this issue, it has been employed a
[2]
biaryl motifs. However, these methods usually require pre-
functionalization of the coupling partners including multiple
[3]
[8]
synthesis processes. In recent years, a direct CÀ H arylation of
heterocycles has developing as a step-economical and environ-
mentally friendly approach to build the heterobiaryl motifs,
where typical catalysts are noble metal species such as
steric bulk of ligands, but the complex syntheses strongly
hamper its application. More recently, Canivet et al. reported Ni-
catalyzed regioselective CÀ H arylation of benzothiophenes
[9]
using bipyridine ligand. This non-noble metal-based catalyst
shows excellent catalytic performances, but difficulty for
separating this catalyst from homogeneous system strongly
hinders its wide application. The solution of this issue is to
[4]
palladium and rhodium. In addition, it still has a challenge to
[5]
regioselectively activate CÀ H of heterocycles in these cases.
Thus, it is strongly desirable to develop non-noble metal-based
catalysts for directly regioselective CÀ H arylation of hetero-
cycles.
[15]
develop highly efficient heterogeneous catalysts.
Porous organic polymers (POPs) have been explored as a
new type of porous materials for applications in gas storage
[10]
and separation, catalysis, and optoelectronics. In particular,
POPs also show great opportunities as heterogeneous catalysts
due to their high permanent porosity, excellent chemical
[
[
[
a] Y. Tang, S. Wang, Dr. F. Chen, Prof. X. Meng, Prof. F.-S. Xiao
Department of Chemistry
Zhejiang University
Hangzhou, 310028 (P. R. China)
E-mail: mengxj@zju.edu.cn
[11]
stability, and flexible molecular design. Recently, we have
successfully synthesized the porous organic phenanthroline-
based polymer (POP-Phen) via a free radical polymerization of
fsxiao@zju.edu.cn
[12]
b] Z. Dai
vinyl-functionalized phenanthline monomers, which offers a
possibility to design and construct the POP-Phen@Ni by
introducing the Ni species into the porous polymer as a
heterogeneous catalyst for regioselective CÀ H arylation. As
expected, the POP-Phen@Ni exhibits excellent catalytic per-
formances (87.4% yield and >99.9% regioselectivity) and
superior recycling ability in a series of regioselective CÀ H
arylations.
Key Laboratory of Surface & Interface Science of Polymer Materials of
Zhejiang province
Department of Chemistry
Zhejiang Sci-tech University
Hangzhou 310018 (P. R. China)
c] Prof. F.-S. Xiao
Key Lab of Biomass Chemical Engineering of
Ministry of Education and College of Chemical and Biological Engineering
Zhejiang University
Hangzhou 310027 (P. R. China)
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/asia.202100695This manuscript is part of a special
collection on Supramolecular Catalysis and Catalyst Immobilization.
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Results and Discussion
The phenanthroline-based porous organic polymer was synthe-
sized from hydrothermal polymerization of vinyl-functionalized
[12]
1
.10-phenanthroline monomer. With the assistance of azobisi-
sobutyronitrile (AIBN), the monomers were quantitatively con-
verted to the corresponding porous polymer (POP-Phen) by
using DMF as a porogenic solvent in autoclave at 100°C for
2
4 h (Scheme S1). The successful preparation of POP-Phen was
1
3
verified by C magic-angle spinning (MAS) NMR spectrum. As
shown in Figure S1 and Figure S2, the disappearance of the
peaks related to the vinyl groups in the range from 110 to
1
20 ppm and the concomitant appearance of the strong peak
at 40.4 ppm assigned to the polymerized vinyl groups, confirm
the successful transformation from the monomers into a highly
polymerized polymer. N2 sorption isotherms (Figure S3 and
Figure S4) indicate that the POP-Phen is highly porous with a
2
À 1
BET surface area and pore volume of 995 m g
and
3
À 1
1
.16 cm g (Table S1, entry 1).
Variation of the molar ratio (x) of POP-Phen and
NiCl (glyme) were prepared from the reaction of POP-Phen with
2
NiCl (glyme) in DMF, and the polymer-supported Ni catalysts
2
were obtained after washing with MeOH and dried under
vacuum condition, which were designated as POP-Phen@Ni-x
(
x=1, 2, 5, and 10). The morphology of the POP-Phen@Ni-x is
Figure 1. (A) N sorption isotherms, (B) SEM image, and (CÀ F) SEM-Mapping
2
images of the POP-Phen@Ni-2.
examined by scanning electron microscopy (SEM) and all of
them show the rough surface (Figure S5-S8). The porous
structure of POP-Phen has been well remained after the
metalation and all of them exhibit high surface areas in the
range of 445–834 m g , as indicated by the N sorption
isotherms (Figure 1A, Figure S9-S12, and Table S1). For example,
POP-Phen@Ni-2 gives the BET surface area at 595 m g (Fig-
ure 1A, green) with hierarchical porosity (Figure S9). SEM-
elemental mapping shows that the POP-Phen@Ni-2 exhibits a
uniform distribution of C, N, Cl, and Ni (Figure 1CÀ F), suggesting
that the Ni species are highly and uniformly dispersed in the
POP-Phen, which are well consistent with that it is undectable
the signal of Ni nanoparticle in XRD pattern (Figure S13).
obtained. Moreover, in the absence of POP-Phen@Ni-2 or
LiHMDS, no product was observed, indicating the important
roles of the catalyst and LiHMDS. When 1.4-dioxane or THF was
used, the product yield drastically dropped from 87.4% to
<1.0% (Table S2, entries 6–7). This abnormal phenomenon
might be related to the change for LiHMDS in different solvent.
The LiHMDS is nonpolar dimer in toluene but polar monomeric
species in 1.4-dioxane or THF. As a result, LiHMDS is easier to
enter the porous organic polymer in toluene than that in the
2
À 1
2
2
À 1
[14,15]
others.
To evaluate catalytic performance of POP-Phen@Ni as a
heterogeneous catalyst, direct CÀ H arylations of benzothio-
phene with aryl halides are chosen as models due to its
importance for organic synthesis especially for pharmaceuticals,
as presented in Table 1. Very interestingly, the 2-phenylbenzo-
thiophene was obtained with 87.4% yield and higher than
To understand the importance of LiHMDS and the reaction
mechanism, we designed deuterium scrambling experiments to
gain deeper insights into the CÀ H activated steps of benzothio-
phene, as monitored by NMR technology. When LiHMDS
(2.2 equiv.) reacted with benzothiophen (1.0 equiv.) at 120°C in
6 mL of toluene for 180 min and quenched with deuterated
methanol (MeOD), only a trace of deuterated benzothiophene
was detected (Figure S14, red); When LiHMDS (2.2 equiv.)
reacted with benzothiophen (1.0 equiv.) in the presence of N-
deuterated hexamethyldidilazane (D-HMDS, 1.0 equiv.) for dif-
9
9.9% regioselectivity for the arylation of benzothiophene at
the C2 position (Table 1, entry 1a). By comparison, NiCl (glyme)
2
only gave a yield of 37.5% and Ni(Phen)Cl gave a yield of
2
6
5.3% (Table 1, entries 1b and 1c). In addition, the nonporous
1
POP-Phen@Ni-2 shows a yield of 57.7% (Table 1, entry 1d).
Possibly, higher yield of the POP-Phen@Ni-2 than that of the
others was reasonably related to its high surface area and
hierarchical porosity, which are favorable for the adsorption
and mass transfer of reactants (1.0 g of POP-Phen@Ni-2 could
adsorb 4.6 g of iodobenzene at room temperature) or reaction
ferent time (Figure 2A), liquid H NMR analysis shows the yield
up to 38.0% of deuterium incorporation; When the parallel
experiments were performed starting from the benzo[b]
1
thiophene-d , LiHMDS, and H-HMDS, liquid H NMR analysis
1
shows 52.0% yield of proton incorporation (Figure 2B). These
results indicate that LiHMDS is able to activate the CÀ H bond of
benzothiophene, forming lithiated benzothiophene species, but
[13]
intermediate, in good agreement with those in literature.
When K PO , K CO , CH COOK, t-BuOLi, and t-BuOK were
[
15]
only a small amount of the species existed in the toluene.
3
4
2
3
3
employed (Table S2, entries 1–5), no desired product was
However, the lithiated species is constantly consumed and
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Table 1. POP-Phen@Ni-2 catalyzed regioselective CÀ H arylation of hetero-
[
a]
arenes with aryl halides.
Entry Product
[b]
[c]
Yield [%]
87.4[
Regioselective [%]
1
1
1
1
a
b
c
99.9
99.9
99.9
99.9
d]
37.5
[e]
65.3[
f]
d
57.7
2
75.6
99.9
3
74.1
69.6
99.9
4
99.9
5
6
7
74.0
72.1
77.8
99.9
99.9
99.9
Figure 2. Time-dependent evolution of the LiHMDS mediated H/D exchange
1
of (A) benzothiophene and (B) benzo[b]thiophene-d .
8
72.0
99.9
selective in the heterogeneous catalysis. As shown in Figure 3A,
the yield increased with increasing Phen-Phen/Ni molar ratios
from 1 to 2 but slightly dropped increasing POP-Phen molar
ratios from 2 to 10. As shown in Figure 3B, the yield increased
with increasing LiHMDS, but decreased with increasing iodo-
benzene (Figure 3C). Figure 3D shows the suitable volume of
toluene.
With the optimal reaction in hand, we set out to evaluate
scope of aryl halides at first, providing corresponding product
in high regioselectivity and high yields (Table 1). In general, the
electron-donating substituents and polysubstituents on the
phenyl ring of aryl iodides such as methoxyl and methyl groups
provide high product yields and more than 99,9% regioselectiv-
9
1
1
1
1
1
1
73.6
80.3
99.9
99.9
99.9
99.9
99.9
99.9
99.9
0
1
2
3
4
5
[g]
12.1
60.1
39.8
29.7
56.1
[
a] Reaction conditions: all of the reactants were purchased and used
without further purification. aryl halides (1.0 mmol), LiHMDS (2.2 mmol),
toluene (6 mL) and POP-Phen@Ni-2 (0.02 mmol), 120°C, 20 h; [b] isolated
yield; [c] regioselectivity for the arylation of benzothiophene at the C2
2 2
position; [d] NiCl (glyme) was used as catalyst; [e] Ni(Phen)Cl was used as
catalyst, the molar ratio of Phen to Ni was 2; [f] nonporous POP-Phen@Ni-
was used as catalyst; [g] 4-bromotoluene was used as reactant.
2
reformed during the reaction process, thus promoting the
reaction (Scheme S2). When t-BuOLi and t-BuOD were em-
ployed, only a trace of deuterium incorporation was detected
(Figure S14, blue), indicating that the inability of t-BuOLi to
generate lithiated benzothiophene species so as inability to
promote the CÀ H arylation reaction.
It is found that the molar ratio of the ligand to metal species
is important for the reaction. Given the excellent spatial
continuity of POP-Phen, it enabled us to finely tune the POP-
Phen/Ni molar ratios to achieve optimal tradeoff of active and
Figure 3. The influence of different parameters on the reaction: (A) molar
ratio of POP-Phen to Ni, (B) the equivalent of LiHMDS, (C) the equivalent of
iodobenzene, and (D) solvent volume.
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ity of C2 position of benzothiophene (Table 1, entries 1a and 2– Conclusion
). When the aryl iodides contain electron-withdrawing groups,
8
it is also obtained excellent yields (Table 1, entries 9–10).
Interestingly, the substituent position on the phenyl ring did
not strongly influence the product yields (Table 1, entries 2–4
and 6–8). However, when 4-bromotoluene was used, the yield
was strongly dropped to 12.1% (Table 1, entry 11) due to more
inactive of aryl bromides than aryl iodides. Next, we turned our
focus to evaluate the different substituents on the benzothio-
phene with iodobenzene. The direct CÀ H arylation of 5-chloro-
In conclusion, we have successfully prepared heterogeneous
catalysts (POP-Phen@Ni) with high surface area, hierarchical
porosity, and excellent stability. In the tests for regioselective
CÀ H activation of heterocycles, the POP-Phen@Ni exhibits
excellent activities and good recyclability. H/D exchange experi-
ments shows that LiHMDS can promote direct CÀ H arylation by
forming the lithiated species. This work might offer a new
opportunity for design of efficient heterogeneous catalysts for
regioselective CÀ H activation of heterocycles.
1
-benzothiophene shows the yield of 60.1% and 100%
regioselective of C2 position (Table 1, entry 12). The catalyst
was also active for 5-methylthianaphthene and 6-bromo-1-
benzothiophene but lower yield (Table 1, entry 13–14). Finally, Experimental Section
when 2-methylthiophene was employed as a reactant, this
reaction afforded 56.1% yield of desired product and 100%
regioselective of C2 site (Table, entry 15). These experimental
results show that this reaction has an exceptionally broad scope
and broaden applications of the POP-Phen@Ni catalyst in the
future.
Synthesis of POP-Phen
[12,17]
The POP-Phen was synthesized according to the literature.
typical run, 3,8-diviny-1,10-phenanthroline (1 g) and AIBN (25 mg)
were dissolved in 10 mL of DMF, followed by heating in an
In a
autoclave at 100°C for 24 h. After washing with CH
Cl and acetone
2
2
and drying under vacuum, it was finally obtained a solid product,
which was designated as POP-Phen.
The recyclability of heterogeneous catalytic system is one of
key factors for industrial applications. Notably, a direct reuse of
POP-Phen@Ni-2 has only a trace of product (Table S2, entry 8),
which might be resulted from the formation of Ni(Phen)(HMDS)
The synthesis of nonporous polymerized phenanthroline was
similar to POP-Phen except that CHCl3 was used as a solvent
instead of DMF.
[16]
x species.
Treatment with sodium borohydride (NaBH ) at
4
5
0°C for 30 min, the used POP-Phen@Ni-2 showed similar
[15]
activity to that of the fresh POP-Phen@Ni-2. After recycling
for 5 times, the POP-Phen@Ni-2 still showed high activity
Synthesis of POP-Phen@Ni-x (x stands for the molar ratio of
POP-Phen to Ni)
(
Figure 4), indicating that the POP-Phen@Ni-2 has a good
A series of porous polymers with different Ni concentrations were
recyclability. Furthermore, we performed a gram-scale reaction
of benzothiophene with iodobenzene, still giving 85.2% of the
prepared from the coordination of POP-Phen and NiCl (glyme). As a
2
typical run, 5 mmol of POP-Phen was swollen in 40 mL DMF,
desired product. In addition, the N sorption isotherms of the
followed by the addition of NiCl (glyme) (2.5 mmol). After stirring at
2
2
room temperature under N atmosphere for 24 h, the mixture was
used POP-Phen@Ni-2 showed similar pore structure to that of
the fresh POP-Phen@Ni-2 (Figure S15-16 and Table S1). These
results suggest the high stability of this catalyst, which also
supported by the hot filtration test.
2
filtered, washed with excessive MeOH and THF, and dried at 50°C
under vacuum, the solid was finally obtained, which was denoted
as POP-Phen@Ni-2.
Synthesis of Benzo[b]thiophene-d1
Benzo[b]thiophene-d
literature.
7
was synthesized according to the
n-Butyllithium (2.5 M solution in hexanes, 30.0 mL,
5.0 mmol, 1.5 equiv.) was dropped to a solution of benzo[b]
1
[18]
thiophene (6.67 g, 50 mmol, 1.0 equiv.) in dry THF (200 mL) at
À 78°C. After stirring for 4 h at À 78°C, D O (40 mL) was added into
2
the mixture. The resulting mixture was warmed to room temper-
ature and stirred for an additional hour. H O was added (50 mL)
2
and the product was extracted with Et O (3*50 mL). The combined
2
organic phase was washed with brine, dried over Na SO , and
2
4
evaporated in vacuum. The product was purified by flash column
chromatography over silica gel (eluent: hexane) to give benzo[b]
thiophene-d1 as a white solid and the deuterium incorporation
1
1
amounted to >99.0% determined by H NMR (Figure S17). H NMR
500 MHz, CDCl , 298 K, TMS): δ 7.83–7.81 (d, 1H), 7.77–7.75 (m, 1H),
(
7
3
.32–7.25 (m, 3H) ppm.
Catalytic Tests
In typical catalysis experiment, benzothiophen (135.2 mg,
Figure 4. Recycling tests of the POP-Phen@Ni-2 in the direct CÀ H arylation
of benzothiophene. Reaction conditions: benzothiophene (1.0 mmol),
LiHMDS (2.2 mmol, 2.2 equiv.), iodobenzene (1.2 mmol, 1.2 equiv.), toluene
a
1
.0 mmol), LiHMDS (380.0 mg, 2.2 mmol, 2.2 equiv), POP-Phen@Ni-2
(11.9 mg) and toluene (6 mL) were added to Schlenk tubes under
(6 mL) and POP-Phen@N-2 (0.02 mmol), 120
°
C, and 20 h.
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N2 atmosphere at 120°C for 20 h. After cooling down to room
temperature, the catalyst was removed from the system by
centrifugation and extracted with ethyl acetate (3*50 mL). The
organic layers were combined, dried over Na SO , and concentrated
Keywords: Porous Organic Polymer · Heterogeneous Catalyst ·
Molecular Ni Catalyst · Regioselective CÀ H activation.
2
4
under reduced pressure, and then purified by silica gel chromato-
graph (petroleum ether) to yield the desired product.
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FULL PAPER
Nickel species have been intro-
duced into porous phenanthroline-
based organic polymer, which is cat-
alytically active, regioselective, and
recyclable for CÀ H activation of het-
erocycles. This work offers a new op-
portunity for design of novel non-
noble metal-based heterogeneous
catalysts for the regioselective CÀ H
activation of heterocycles.
Y. Tang, Z. Dai, S. Wang, Dr. F. Chen,
Prof. X. Meng*, Prof. F.-S. Xiao*
1 – 7
Metalated Porous Phenanthroline-
Based Polymers as Efficient Hetero-
geneous Catalysts for Regioselec-
tive CÀ H Activation of Heteroarenes