A robust heterogeneous Co-MOF catalyst in azide-alkyne cycloaddition and Friedel-Crafts reactions as well as hydrosilylation of alkynes

Article abstract of DOI:10.1039/d0nj04626d

Organic reactions using metal-organic frameworks (MOFs) as catalysts are promising with regard to their environmentally friendly features and potential catalyst recyclability. A robust Co(ii)-MOF {[Co2(l-mac)(4,4-bpt)(H2O)]·3.5H2O}n (1) and its enantiomer {[Co2(d-mac)(4,4-bpt)(H2O)]·3.5H2O}n (2) (l/d-mac = basic forms of l/d-malic acid, 4,4-Hbpt = 3,5-di(pyridin-4-yl)-4H-1,2,4-triazole) have been gram-scale prepared under solvothermal conditions. Structural analysis reveals that mac manages Co(ii) ions to form 1-D chains, which are further extended via 4,4-bpt connectors into a noninterpenetrating 3D framework architecture. It was found that 1 can be as a heterogeneous catalyst for multiple organic reactions, such as azide-alkyne cycloaddition and Friedel-Crafts reactions with good isolated yields and good recycle runs (at least five times without substantial degradation). Additionally, 1 can promote hydrosilylation of alkynes under harsh conditions with moderate yield. This journal is

Full text of DOI:10.1039/d0nj04626d

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DOI: 10.1039/D0NJ04626D
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A Robust Heterogeneous Co-MOFs Catalyst in Azide-alkynes
Cycloaddition and Friedel-Crafts Reactions as well as
Hydrosilylation of Alkynes†
Received 00th January 20xx,
Accepted 00th January 20xx
a‡
a‡
a
a*
a
Tai-Xue Wu, Jun-Song Jia, Wei Luo, He-Dong Bian, ab* Hai-Tao Tang, Ying-Ming Pan, Fu-
DOI: 10.1039/x0xx00000x
Ping Huanga*
Organic reactions using metal−organic frameworks (MOFs) as catalysts are promising with
regard to their environmentally friendly features and potential catalyst recyclability. A robust
Co(II)-MOF {[Co2(L-mac)(4,4-bpt)(H2O)]·3.5H2O}n (1), and its enantiomer {[Co2(D-
mac)(4,4-bpt)(H2O)]·3.5H2O}n (2) (L/D-mac = basic forms of L/D-malic acid, 4,4-Hbpt
= 3,5-di(pyridin-4-yl)-4H-1,2,4-triazole), have been gram-scale prepared under solvothermal
conditions. Structural analysis reveals that mac manages Co(II) ions to form 1-D chains, which
are further extended via 4,4-bpt connectors, into a noninterpenetrating 3D framework
architecture. It was found that 1 can be as a heterogeneous catalyst for multiple organic
reactions, such as azide-alkynes cycloaddition, Friedel-Crafts reactions with good isolated
yields and good recycle runs (at least five times without substantial degradation). Additionally,
1 can promote hydrosilylation of alkynes reaction in harsh condition with moderate yield.
researchers due to their environmentally friendly
features and potential catalyst recyclability. 7-10
Introduction
For example, Zhou and co-workers reported a series
of MOF-catalysts in Knoevenagel condensation
reaction.11 Besides，Jiang and Sun reported some Zn(II)-
MOFs are able to catalyze the cycloaddition of CO2.12
What’s more, Zhang and co-workers reported some
Ni-MOFs are capable of efficiently catalyzing the
alkene hydrosilylation.7
Due to high degree of surface area, well-defined
pore structure, multiple active site and adjustable pore
size, metal organic frameworks (MOFs) have attracted
increasing interest in recent years.1-3 MOFs are capable
of many applications for their tunable local
environment and low density, which further facilitates
mass-diffusion, such as gas sorption/separation,
biomimetics, catalysis etc.2b,4-6 Moreover , in order to
optimize its performance to satisfy the application in
multiple fields, such as catalysis ,various types of
MOFS and their composites are designed, such as (2D)
MOF nanosheets, the micro- and nanoscale MOF
particles and metal-loaded metal–organic frameworks
(metal@MOFs) and so on.7d-e In past decades,
heterogeneous MOF-catalysts in the fields of organic
reaction have aroused great interest of many
However, considering the shape and/or size
limitations of the complexes, some strategies have
been proposed for the development of heterogeneous
MOF-catalysts. One method is to control its
morphology or composition with other functional
materials.9a,13-14 For instance, Dong and co-workers
reported a CuI@UiO-67-IM heterogeneous phase
transfer catalyst for the azide-alkynes cycloaddition
with excellent regioselectivity and yield.13a Another
method is to expand the types of organic reactions. Eg.
Dirk E. De Vos and co-workers reported a Cu/Ni-MOF,
which allows to direct the selectively tandem C-C
bond forming process for the desired pharmaceutical
intermediate.15 Up to now, other than the widely
a
State Key State Key Laboratory for Chemistry and Molecular Engineering of
Medicinal Resources, School of Chemistry & Pharmacy, Guangxi Normal University,
Guilin 541004, PR China. E-mail: huangfp2010@163.com (F.-P. Huang);
httang@gxnu.edu.cn (H.-T. Tang).
investigated
Knoevenagel
reaction16,
CO2
cycloaddition reaction17-18 etc., there are still a lot of
classical organic reactions (eg. Azide-alkynes
Cycloaddition, Friedel-Crafts) and harsh organic
b
School of Chemistry and Chemical Engineering, Guangxi University for
Nationalities, Key Laboratory of Chemistry and Engineering of Forest Products,
Nanning, 530008, P. R. China. E-mail: gxunchem@163.com (H.-D. Bian)
† Electronic supplementary information (ESI) available: Experimental details,
general characterization, additional plots and discussion. CCDC number: 1977363
and 1977364. For ESI and crystallographic data in CIF or other electronic format
see DOI: 10.1039/x0xx00000x
‡ These authors contributed equally.
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reactions (eg. the Hydrosilylation of Alkynes), have dichroism (CD) spectra were recorded on aViJeawsAcrtoicleJ-O7n5lin0e
not been widely explored in-depth when using simple spectropolarimeter using KBr pelDleOtIs: 1.0.M103i9c/rDo0mNJe0r4i6t2i6cDs
but easily-prepared heterogeneous MOF-catalysts.
Herein,
bpt)(H2O)]·3.5H2O}n (1) and its enantiomer {[Co2(D-
mac)(4,4-bpt)(H2O)]·3.5H2O}n (2), have been gram-
scale prepared under solvothermal conditions (L/D-
mac = basic forms of L/D-malic acid, 4,4-Hbpt = 3,5-
ASAP 2460 Version 3.00 was used for N2 adsorption
novel Co(II)-MOF {[Co2(L-mac)(4,4- (Figure S6).
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Synthesis of {[Co2(L-mac)(4,4-bpt)(H2O)·3.5H2O}n
(1).
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1 was prepared under solvothermal conditions. A
mixture of Co(NO3)2·6H2O (145 mg, 0.5 mmol), 4,4′-
Hbpt (112 mg, 0.5 mmol), L(-)-H3ma (67 mg, 0.5 mmol),
NaOH (40 mg, 1 mmol), water (7 mL), and methanol
(7 mL) was placed in a 23 mL Teflon-lined stainless
steel vessel and heated at 160 °C for 48 h and then
cooled to room temperature at a rate of 5 °C, and
finally the red strip crystalline products of 1 were
obtained by washing it with distilled water and
methanol, then picking out after being dried in air.
Yield: 70 % (base on Co(II)). Elemental analysis (%):
Calcd: C, 34.77; H, 3.62; N, 10.87. Found: C, 34.73; H,
3.65; N, 10.90. IR (KBr, cm-1): 3404m, 1609m,
1546s,1426m, 1313w, 1201w, 1087w, 841 m, 749w, 630w.
di(pyridin-4-yl)-4H-1,2,4-triazole,
respectively).
Structural analysis reveals that the 3D framework
architecture with two types of open windows (ca.
13.445(4) × 13.445(5) Å and 6.365(45) × 6.365(45) Å). 1
can be used as a heterogeneous catalyst to promote
not only the azide-alkynes cycloaddition from
corresponding benzyl bromide ， sodium azide and
terminal alkynes as a sequential procedure, but also
the Friedel-Crafts reaction of indoles with trans-β-
nitrostyrenes resulting good isolated yields and recycle
runs (at least five times without substantial
degradation in crystallinity and catalytic activity).
Additionally, 1 can promote hydrosilylation of alkynes
reaction in harsh condition with moderate yield and
selectivity.
Synthesis of {[Co2(D-mac)(4,4-bpt)(H2O)·3.5H2O}n
(2).
2 was synthesized similarly to compound 1 except
using D (-)-H3mac (67 mg, 0.5 mmol) instead of L (-)-
H3mac (67 mg, 0.5 mmol), and red strip crystalline
products were obtained in a 69% yield (base on Co
(II)). Elemental analysis (%): Calcd: C, 34.77; H, 3.62; N,
10.87. Found: C, 34.79; H, 3.59; N, 10.85. IR (KBr, cm-1):
3406m, 1597m, 1558s,1426m, 1315w, 1197w, 1086w, 843
m, 745w, 587w.
Experimental section
Materials and Instrumentation.
The reagents and solvents employed were
commercially available and used as received without
further purification. THF, toluene, hexane, ethyl ether,
DCM, and CH3CN dried by molecular sieve were used.
Column chromatography on silica gel (300-400 mesh)
was carried out with technical grade 60-90 ℃
petroleum ether (distillated before use) and analytical
grade EtOAc (without further purification). H and C
spectra were recorded on a 400 MHz spectrometer
and chemical shifts were reported in ppm. HNMR
General procedure azide-alkynes cycloaddition
reaction catalyzed by 1.
1
13
Mixed solution NaN3 (2 mmol), ArCH2Br (1 mmol),
and 1 (0.02 mmol) in H2O (2 mL) was heated at the 60 ℃
for 2 h and stirred for another 4 h after addition of
alkynes (1.5 mmol). Once the reaction finished, H2O (3
mL) and CH2Cl2 (5 mL) were added and Co-MOF of 1
was recovered by filtration. The organic phase was
separated and aqueous phase was extracted with
CH2Cl2 (3 × 5 mL). The organic fractions were
combined, dried (MgSO4), filtered through filter paper,
and concentrated in vacuo. The crude reaction
product was purified by column chromatography
(300-400 mesh silica gel, 30 mm Ø, pentane: Et2O 10:1)
to give the 1,2,3-triazoles.
1
spectra was referenced to CDCl3, and 13C-NMR spectra
was referenced to CDCl3 (77.0 ppm). Peak
multiplicities were designated by the following
abbreviations: s, singlet; d, doublet; t, triplet; m,
multiplet; brs, broad singlet and J, coupling constant
in Hz. The C, H, and N microanalyses were carried out
with a Perkin–Elmer PE 2400 II CHN elemental
analyzer. The FT-IR spectra were recorded from KBr
pellets in the range 4000-400 cm-1 on a Perkin–Elmer
one FT-IR spectrophotometer. X-ray powder
diffraction (XRPD) intensities were measured at 293 K
on a RigakuD/max-IIIA diffractometer (Cu-Kα, λ =
1.54056 Å). The crystalline samples were prepared by
crushing the single-crystals and scanned from 3-60° at
a rate of 5 °/min. Calculated patterns of 1-2 were
generated with Powder Cell. The solid-state circular
General procedure for the Friedel–Crafts
alkylation reaction of trans-β-Nitrostyrene and
indoles catalyzed by 1.
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Under the protection of Ar, trans-β-nitrostyrenes dimeric units are linked by carboxylate groups in mac
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(0.2 mmol), indoles (0.3 mmol) and 1 (0.01 mmol) ligands to generate a helix chain DrOuI:n1n0.i1n03g9/Da0loNnJ0g46t2h6De
were added to a 25 mL flask, then CH2Cl2 (1 mL) was crystallographic c axis. (Fig. S1 in the Supporting
added. The reaction was performed at 35 ℃ for 24 h. Information)
Co-MOF (1) was recovered by filter and the organic
phase was concentrated in vacuo. The crude product was
purified by column chromatography (300-400 mesh silica
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gel, 30 mm Ø, pentane: Et2O 15:1) to give the indole
derivatives. 19-20
General procedure for selective hydrosilylation of
alkynes catalyzed by 1.
A 25 mL flame-dried flask was cooled under dry Ar
atmosphere, then Co-MOF (1) (0.02 mmol), THF (2.0
mL), PhSiH3 (2.0 mmol) were added successively.
Scheme 1. Preparation of chiral enantiomers 1- and 2-
After that, the mixture was injected with NaBHEt3 (1.0
MOF and their coordinate environment diagrams.
M) (60 μL, 0.06 mmol) by dropwise and then the alkyne
These chains are further connected by 4,4′-bpt
(1.0 mmol) was injected, reaction at 50 ℃ for 4 h. The
ligands to generate a noninterpenetrating 3D open
resulting solution was added 10 mL of ether and filtered
framework with two types of open windows consists of
several circular micropores and chiral triangular pores
(the size of ca. 13.445(4) × 13.445(5) Å and 6.365(4) ×
6.365(4) Å, respectively.) which as the basic active
sites. (Fig. 1 and Fig. S2). Better insight into this
framework can be achieved by topology analysis.
Considering the coordination modes of metal atoms,
mac and 4,4′-bpt, which are all viewed to be 4-
connected nodes, respectively. Thus, a novel four-
connected topology in 1 with the short Schläfli symbol
of (43.83)2(42.84) (4.85) could be observed.22 The chiral
nature of the enantiomorphs 1-2 was further
confirmed by solid-state CD spectra. The spectrum for
a bulk sample of 1 displays two negative peaks at 482,
525 nm and a positive peak at 583 nm, while that for 2
is approximately the mirror image of 1 (Fig.S4).
through filter paper to recover Co-MOF (1). The combined
filtrates were concentrated and selectivity was monitored
by 1H NMR analysis. The crude mixture was purified by
column chromatography (300-400 mesh silica gel, 30
mm Ø, pentane as eluent) to get the corresponding
product. 21
Results and discussion
Crystal structure
As shown in Scheme 1, 1/2 was generated from a
mixture of malic acid, pyridin-triazole ligand and
Co(NO3)2 under solvothermal conditions. 1 and 2 are
revealed
enantiomorphs
through
the
X-ray
crystallographic studies, then the structure of 1 to be
described in detail as a representative (1 and 2 with
removal of solvent molecules is 28.1% and 28% of the
cell volume calculated by PLATON). 1 crystallized in
the hexagonal system with chiral space group P63. The
asymmetric unit of 1 contains two independent Co(II)
cations. Co1 is six-coordinated, showing an octahedral
environment, four carboxylate O atoms (O1, O2, O3
and O5) composing the equatorial plane and two
pyridyl N donors (N3 and N5) occupying the apical
plane led to the formation of an octahedral
environment, the corresponding bond lengths are Co–
N=2.112(3)-2.114(3) Å and Co–O = 2.003(3)–2.371(3) Å,
respectively. Co2 is bonded by two pyridyl N atoms
(N1 and N4) and four carboxylate/water O atoms (O2,
O3, O4, and O6) that displays a similar coordination
octahedral environment. The Co2 is linked to Co1
through one mac hydroxyl O atom and one trizole N-
N bridge to form a dimeric unit with Co1•••Co2 =
3.122(3) Å and Co1-O3-Co2 = 102.0(2) º. The {Co2}
This journal is © The Royal Society of Chemistry 20xx
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DOI: 10.1039/D0NJ04626D
(a)
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60℃
As prepared
Simulated
Fig 1. The triangular-like window (a), circular-like
window (b) and the nonpenetrating 3D framework
structure of 1 (c) and their schematic diagram of
surface channel for solvent access (d), the Structure of
1 showing the view of the 3D architecture(e) and its
schematic description (f).
10
20
2 Theta
30
(b)
(c)
THF
pH=11
pH=10
pH=9
MeOH
The Stability of MOFs 1 and 2
CH3CN
pH=8
pH=7
pH=6
pH=5
The Co-MOFs of 1/2 is expected to be a promising
candidate to serve as a stable heterogeneous catalyst
to facilitate some organic reactions.23 The Co-MOFs
can keep stable in common solvents media, and the
coordinated water molecules can be removed during
activation then leaving open metal sites to participate
in the catalytic reaction as lewis acid.24 The high
stability and the action of lewis acid are expected to
combine to form an attractive multifunctional porous
preference material. As shown in Fig. 2, Fig. S3, by the
means of TG analyses, FTIR spectra and in-situ
powder XRD measurements, the thermal stability of
the crystalline Co-MOF material was evaluated. The
TG curve of 1-2 suggested that the observed weight
loss of ca. 14.9 % between 60 and 160 °C corresponds
to the dehydration process. The framework started to
decompose around 420 °C (Fig. S3a.). After activated
samples at 160 ℃ for 24h, as can be seen from Fig. S3e,
f, the solvent molecules of the activated samples were
significantly removed with the frame of 1 remained
stable. In addition, the PXRD pattern of desolvated
samples is as sharp as the as-prepared 1/2 after heating
under vacuum for 24 h, which confirms the framework
is stable after losing the lattice/coordinated water
molecules (Fig. 5 and Fig. 6a). The PXRD patterns of
samples immersed in different solvent for about 24 h
(eg. H2O, MeOH, EtOH, DMSO, THF, CH3CN, etc.) or
different acid/base condition (pH = 2-11), are almost
the same as the as- prepared 1/2, which demonstrates
the stability of solvent and acid/base.
EtOH
H2O
pH=4
pH=3
pH=2
DMSO
Simulated
Simulated
10
20
30
10
20
2Theta
30
2Theta
Fig 2. The XRD patterns of 1 at different temperatures
(a), after immersing in different solvents (b) and
different acid/base condition (c).
Azide-alkynes Cycloaddition Reactions Catalyzed
by 1
The 1,2,3-triazoles have found wide used in
industrial applications such as dyes, corrosion
inhibition
photostabilizers,
(of
copper
photographic
and
copper
materials,
alloys),
and
agrochemicals.25 Therefore, it is very necessary to
develop new and more efficient catalyst to a diverse
array of 1,2,3-triazole pharmacophores. The catalytic
properties of 1/2 for the azide-alkynes cycloaddition
reactions were evaluated in the follow.
To initiate our investigations, 4-tert-butylbenzyl
bromide reacts with sodium azide to obtain
intermediate A in 2 h. In the case of A without
separation, the “one-pot” protocol of directly adding
4-bromophenylacetylene to obtain 1,2,3-triazole
compound 5 and 5’ at the 4 h in the present of 2 mol%
catalyst 1 (Scheme 2). The structure of a representative
product 5 was unambiguously confirmed by X-ray
crystallographic analysis (see ESI). Gratifyingly, the
value of the yield 5:5’ is 4.4:1, which indicates the
MOF-catalyst shows regioselective to the azide-
alkynes cycloaddition reaction. We also investigated
the reaction temperature and time (Table S1), and
finally obtained 5 + 5’ with 77 % with the isolated yield
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(Weighing yield after separation and purification by Fig 3. The leaching test of azide-alkynes cyVcielwoaArdticdleiOtinolinne
column chromatography) and the TON (turnover reaction (left) and Friedel–Crafts DaOlkI:y10la.1t0i3o9n/D0rNeJa0c4t6i2o6nD
number) value is 39.
(right).
5
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80
70
60
50
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30
20
10
0
N
80
70
60
50
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10
0
N
N
tBu
Br
NaN3
Br
5
Br
Co@MOF
H2O
4
N3
9
tBu
tBu
N
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N
3
A
N
tBu
Br
5'
1
2
3
4
5
1
2
3
4
5
Scheme 2. The process of azide-alkynes cycloaddition
reaction catalyzed by 1.
Runs
Runs
Fig 4. Recycling test of azide-alkynes cycloaddition
reaction (left) and Friedel–Crafts alkylation reaction
(right).
To investigate whether the catalytic activity will be
affected by an excess of heterogeneous catalyst, 1, 4-
tert-butylbenzyl
bromide
and
4-
bromophenylacetylene were chosen as substrates to be
a model reaction. We separated the organic matter by
filtration after 30min, then the filtrate was stirred for a
further 1.5 h, 3 h, 4.5 h, and 6 h. As shown in Fig. 3 (left:
catalyst filtration), no obvious conversion of 1,2,3-
triazoles compound is observed by GC-MS. At the
same time, a control trial under the same conditions
without filtration the catalyst was evaluated as shown
in Fig. 3 (left: no filtration) and the catalytic
conversions in the absence of 1 was tested Fig. 3 (left:
no catalyst). Therefore, the conclusion that 1 is a
heterogeneous catalyst can be drew. In practice, the
separability and reusability are the key parameters to
evaluate heterogeneous catalysts. Here, the reusability
and stability of 1 were further studied with 1,4-tert-
butylbenzyl bromide as substrate. Within 6 h (2 + 4 h),
the amount of 5 remains the same, which indicates
that the catalytic process had been completed to some
extent. Subsequently, the regenerated 1 was collected
by filtration, then washed 3 times with methanol after
that dried naturally at room temperature for the next
use. As illustrated in Fig. 4 (left), we studied the
regenerated catalytic efficiency of 1. After 5 runs, the
conversion efficiency was reduced by about 9 % but
still retained a good value. Besides, we can observe
that the crystalline structure of 1 was maintained after
5 runs (Fig. 5 (left)). These indicated that 1 suggested
high efficiency in the azide-alkynes cycloaddition
After 5 catalytic run
After 5 catalytic run
After 3 catalytic run
After 3 catalytic run
After activation at 160℃
After activation at 160℃
As prepared
Simulated
As prepared
Simulated
10
20
2 Theta
30
10
20
2 Theta
30
Fig 5. PXRD patterns of as-synthesized 1 and after
three and five catalytic runs for the reactions of azide-
alkynes cycloaddition reaction (left) and Friedel–
Crafts alkylation reaction (right).
Using our optimized experimental conditions, the scope
of the MOF-catalyzed formation of 1,2,3-triazoles was
examined. The results are summarized in Table 1. First,
we used benzyl bromide as the reaction substrate to
investigate the electronic effects of alkynes. Both 4-
methylphenylacetylene and 4-fluorophenylacetylene can
react with benzyl bromide to obtain the target product
1,2,3-triazoles with moderate to good yield (entries 1-2,
Table 1). In addition, para- large steric substituted
arylalkyne, 4-tert-butylphenylacetylene, which could
smoothly react with benzyl bromide and provided the
corresponding product in 70% isolated yield (entry 3,
Table 1). Subsequently, we explored the reaction of 4-
tert-butylbenzyl bromide with phenylacetylene and 3-
methoxyphenylacetylene, where both obtained desired
products in good yield (entries 4-5, Table 1).
Compared with the reported complicated catalysts of
CuI@UO-67-IM by Dong's group and PEG-tris-trz-
CuI by Astruc’s groups, there are rarely reported easy-
prepared pure MOFs with considerable catalytic effect,
for this rection.13 (a),26
reaction and can be regenerated easily and directly.
80
catalyst filtration
no filtration
no catalyst
catalyst filtration
no filtration
80
70
60
50
40
30
20
10
0
70
60
50
40
30
20
10
0
no catalyst
Table 1. Substrate Scope for the Reaction of Benzyl
Azide and Alkynes.a
-10
0
5
10
15
20
25
0
1
2
3
4
5
6
T℃ h℃
T℃ h℃
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Page 6 of 12
ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
R
View Article Online
DOI: 10.1039/D0NJ04626D
Co
N
N
R
L
R'
L
S
N
R
Entry
3
4
Isolated yield of 5+5’/ %
N
1
R'
Co
N
N
4
O
H
5'
H3O
S
5
1
H3O
H
Co
Co
Co
Co
Co
H3O
L
L
S
B
S
1
68
71
Co
R
R
R'
N
N
A
N
N
N
N
E
R
N3
R'
E'
F
2
3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Co
Co
Co
Co
Co
Co
L
S
L
S
L
S
or
N
R'
N
R'
tBu
N
R'
70
R
N
N
N
N
N
N
R
R
D'
C
(minor)
D
(major)
N
4
74
O
*
O
Co
Co
Co
N
O
L
N3
S
MeO
N
N Co
tBu
O
5
75
77
O
N
Br
6
Scheme 3. The possible mechanism of azide-
alkynes cycloaddition reaction by catalyst 1.
a
Reaction conditions: benzyl halide (1 mmol), NaN3
(1.5 mmol), H2O (2 mL), Co-MOF (0.02 mmol),
temperature (60 °C), alkynes (1.5 mmol) and reaction
time (2 + 4 h).
Friedel–Crafts Alkylation Reaction of trans-β-
Nitrostyrenes and Indoles Catalyzed by 1
As shown in Scheme 3, based on the experimental
results and previous literature reports, we proposed a
possible
cycloaddition reaction catalyst by 1. First, catalyst 1
combined with alkynes 4 to furnished acetylide-MOF
complex B along with release a molecule H3O+.
Followed by smoothly interacts with azide compound
Friedel-Crafts alkylation reaction of indoles with
trans-β-nitroalkenes is one of the most important
paths for preparing tryptamine and its derivatives.30
Different synthetic strategies and new heterogeneous
catalysts have been proposed to access this type of
compounds, so we further examined the activity of 1
for the reaction of Friedel–Crafts alkylation.
mechanism
of
the
azide-alkynes
A
afford intermediate C.27 The formation of
In order to expand the application range of catalyst
1, we explored the catalytic performance of catalyst 1
for Friedel–Crafts alkylation reaction. Under an
atmosphere of Ar, the indole derivative 8 was obtain
in 56% isolated yield upon treatment of a 1: 1.5 mixture
of (E)-(2-nitrovinyl) benzene (6) and 5-methoxy-2-
methyl-1H-indole (7) with 10 mol% 1 in CH2Cl2 at 35 ℃
for 12 h. We explored the relationship of reaction
solvent and time to determine the standard condition:
trans-β-nitrostyrenes (0.2 mmol), indole (0.3 mmol),
MOF 1 (0.01 mmol) in a solution of CH2Cl2 at 35 ℃ for
24 h. The indole derivative 8 was obtained with an
isolated yield of 70% and thus the TON value is 70.
intermediate C favors the alkyne carbon atom
nucleophilically attack the nitrogen atom at the end of
the azide.28 Subsequently, alkyne and azide
compounds undergo a cycloaddition reaction to
obtain intermediate D or D’.29 Compared with D and
D’, the steric hindrance between R and MOF, R and R’
in D’ is greater than D, which leads to the
predominance of intermediate D. Subsequent ring
contraction of the generated D/D’ would lead to
intermediate E/E’. Finally, E/E’ abstracts a proton
from H3O+ that obtained the desired 1,2,3-triazole
product and followed by regeneration of the 1
completes catalytic cycle.
Similarly,
a
leaching test (Fig. 3, right) and
recyclability experiment (Fig. 4, right) and the
catalytic conversions in the absence of 1 was tested Fig.
3 (right: no catalyst) were performed as mentioned
above.
After five cycles, the conversion efficiency was
slightly reduced (about 6 %) but still retained a good
yield, and we tested the PXRD of MOF 1 and found the
crystalline structure of 1 had no significant change as
shown in Fig. 5 (right). Therefore, we can draw the
6 | J. Name., 2012, 00, 1-3
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New Journal of Chemistry
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Journal Name
conclusion that 1 suggested high efficiency in the
Friedel–Crafts alkylation reaction and can be
regenerated easily and directly.
ARTICLE
1
2
3
4
5
6
7
8
1
2
View A4rti3cle Online
DOI: 10.1039/D0NJ04626D
N
H
64
N
NO2
MeO
3
4
70
MeO
N
H
NO2
Co-MOF(0.01mmol)
35 o
+
NO2
R3
9
MeO
N
C
H
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
N
45
N
H
H
6
7
8
Scheme 4. The process of Friedel–Crafts alkylation
reaction of trans-β-Nitrostyrenes and Indoles
catalyzed by 1.
5
6
63
N
MeO
NO2
68
N
H
Cl
Using 1 as the catalyst, we then examined the scope
of this Friedel–Crafts alkylation with indoles (Table 2).
For the purposes of convenience, reaction conditions
always refer to standard conditions mentioned above.
First, with (E)-(2-nitrovinyl) benzene as the trans-β-
nitrostyrene substrate, we explored four electron-rich
indoles with different substitution positions. As shown
in Table 2, indole can make a certain degree
improvement of isolated yield, and especially
improved to 64% when the 1-position of indole was
substituted by methyl (entry 2, Table 2), which shows
that the electron-donating group on indole is
conducive to product formation. The indole derivative
5-methoxy-2-methyl-1H-indole with two electron-
donating groups yields the target product in a 70%
isolated yield, which also shows that the more
electron-rich the indole in this catalytic system, the
more favorable the transformations (entry 3, Table 2).
We then changed the substrate (E)-(2-nitrovinyl)
benzene to (E)-1-chloro-2-(2-nitrovinyl) benzene with
an electron-withdrawing group and made reactions
using three indoles with electron-donating groups to
obtain the target product, which results in a good
yield (entries 5-7, Table 2). We examined the reaction
between (E)-1-fluoro-4-(2-nitrovinyl) benzene and 1-
methyl-1H-indole, which afforded lower yields desired
product (entry 8, Table 2). We found that trace yields
or no reactions were obtained whether electron-
deficient indole was used to react with trans-β-
nitrostyrene or electron-donated trans-β-nitrostyrene
was reacted with indole (entries 9-10, Table 2).
Compared with the reported catalyst,31 MOFs 1 can
promote the reaction under mild conditions (shorter
reaction time, lower temperature and no cocatalyst)
and expanded wide scope of substrates with a good
catalytic activity.
7
51
N
MeO
H
NO2
8
40
N
F
Br
NO2
9
0
N
Cl
NO2
10
trace
N
MeO
a
Reaction conditions: trans-β-nitrostyrenes (0.2
mmol), indoles (0.3 mmol), CH2Cl2(1 mL), Co-MOF
(0.01 mmol), 35 °C, 24 h.
According to the experimental result and
conducting a wide literature survey, a possible
mechanism Scheme
5
was proposed. Trans-β-
nitrostyrene and coordinate water in the MOF form a
H-bond, increasing the electrophilic character of the
aliphatic carbon atom and thus favors the attack from
the indole.32 Indole interaction with the carbonyl
oxygen in the MOF form a H-bond not only increases
the nucleophilicity but also brings two substrates
efficiently close for the formation of the alkylated
product (Scheme 5, F).31a There is no H-bond between
1-methyl-1H-indole and the carbonyl oxygen in the
MOF, but the electron donating effect of methyl also
enhances the nucleophilic ability of indole.33 Trans-β-
nitrostyrene and indole undergo nucleophilic addition
reaction to obtain intermediate G. The generated
intermediate
hydrogen transfer to afford the expected product 8.
G
underwent to the subsequent
Table 2. Substrate Scope for the Reaction of trans-β-
Nitrostyrenes and Indoles. a
Isolated yield
Entry
6
7
of 8/ %
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Page 8 of 12
ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
Ph
R
View Article Online
NaBHEt3(6 mol%)
Co-MOF(0.02 mmol)
9
+
NO2
DOI: 10.1039/D0NJ04626D
R
SiH2Ph
SiH2Ph
R
+
R
+
N
PhSiH3
R
SiH2Ph
11
+
R
SiH2Ph+
R
SiH2
Ph
N
2 equiv.
N
or
12
13
14
Ph
15
10
H
R
R = H or Me
N
N
Ph
O
N
O
8
+
H
O
H
N
H
O
Table 3. Substrate Scope for the Reaction of
H
O
*
N
N
H
O
O
H
O
*
H
O
*
Hydrosilylation of Alkynes. a
O
O
O
Co
O
N
O
Co
Co
N
O
N
O
N
N Co
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Isolated yield Ratio of
of 11-15 /% 11:12:13:14:15
N
N Co
O
N
N Co
O
Entry
9
10
O
O
O
O
N
N
N
1
52
16
51:32:13:3:1
54:26:12:4:4
-
F
G
2
PhSiH3
Scheme 5. The possible transformation mechanism of
Friedel–Crafts alkylation reaction by 1.
MeO
3
trace
Selective Hydrosilylation of Alkynes Catalyzed by
1
a
Reaction conditions: alkynes (1 mmol), PhSiH3 (2
mmol), NaBHEt3 (6 mol %), Co-MOF (0.02 mmol),
temperature (50 °C), 6 h.
Organosilanes are important synthetically valuable
skeleton in various fields, such as organic synthesis,
polymer chemistry, and drug discovery.34 We here
intend to explore the possibility of catalyzing the
selective hydrosilylation of alkynes.35
The leaching test, the catalytic conversions in the
absence of 1 and leaching reusability was evaluated
under standard conditions by selecting the
hydrosilylation of phenylacetylene with PhSiH3 as a
model reaction. As shown in Fig 6 (b), when the
reaction progressed to 30 minutes, the catalyst in the
reaction system was removed. After lasted to 6 h, and
the yield was 14%, the yield is much lower than with a
catalyst. In our five cycles experiment, the overall yield
change was within 10% (Fig 6c), which indicates that
no leaching of the catalytically active sites occurs and
that Co-MOF 1 features a typical heterogeneous
catalyst nature. Furthermore, PXRD patterns of as-
synthesized 1 show that the crystalline structure of 1
was maintained after five runs (Fig. 6a). To the best of
our knowledge, there is no report of using MOF as a
catalyst to directly reduce terminal alkynes to obtain
alkyl silicon reagents in one step. The experiment
confirms the potential feasibility of MOFs as a catalyst
for this reaction. Although it is a pity that due to the
space limitation of MOFs, the substrate is not
expanded much, it provides a certain basis for the
application of MOFs in this reaction in the future.
Ph
NaBHEt3(6 mol%)
Co-MOF(0.02 mmol)
9
+
Ph
SiH2Ph
SiH2Ph
Ph
Ph
+
PhSiH3
2 equiv.
Ph
SiH2Ph
11
+
+
SiH2Ph
13
+
Ph
SiH2Ph
12
14
15
10
Scheme 6. Selective Hydrosilylation of Alkynes
Catalyzed by 1
We started our investigations by testing the
hydrosilylation of phenylacetylene with PhSiH3 as a
benchmark reaction. The transformation was initially
achieved in the presence of 2 mol% MOF catalyst 1
6 mol% of NaBHEt3 as an activator in
tetrahydrofuran (THF) at 50 ℃ 。 We obtained five
products with a total yield of 52% and their ratio was
determined as 51:32:13:3 by H NMR. Subsequently, we
screened solvent and temperature of the reaction
(Table S5) to get the optimal conditions: alkynes (1
mmol), PhSiH3 (2 mmol), 1 (0.01 mmol) and NaBHEt3
(6 mol %) in a solution of THF at 50 ℃ for 6 h.
and
1
(a)
(b)
Under standard conditions, we explored the
reaction of 4-methylphenylacetylene with PhSiH3.
Similarly, the result has five kinds of products, the
ratio is 54:26:12:4:4 (entry 2, Table 3). However, 4-
60
50
40
30
20
10
0
catalyst filtration
no filtration
no catalyst
After 5 catalytic run
After 3 catalytic run
After activation at 160℃
methoxyphenylacetylene only obtained
amount of product (entry 3, Table 3).
a
trace
As prepared
Simulated
10
20
30
0
1
2
3
4
5
6
2 Theta
T℃ h℃
8 | J. Name., 2012, 00, 1-3
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New Journal of Chemistry
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Journal Name
(c)
ARTICLE
1
2
3
4
5
6
7
8
Z. Niu, Y. Peng, C. Shan, G. Verma, L. VWiewoArjtticalesO,nliZne.
DOI: 10.1039/D0NJ04626D
Zhang, B. Zhang, Y. Feng, Y. S. Chen and S. Ma, J. Am.
60
50
40
30
20
10
0
Chem. Soc. 2019, 141, 14443.
2 (a) H. Wang, P. Rassu, X. Wang, H. Li, X. Wang, X.
Wang, X. Feng, A. Yin, P. Li, X. Jin, S. L. Chen, X. Ma
and B. Wang, Angew. Chem., Int. Ed. 2018, 57, 16416; (b)
H. Wang, X. Dong, E. Velasco, D. H. Olson, Y. Han
and J. Li, Energy Environ. Science 2018, 11, 1226.
9
10
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45
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51
52
53
54
55
56
57
58
59
60
3 (a) J. L. Sun, Y. Z. Chen, B. D. Ge, J. H. Li and G. M.
Wang, ACS Appl Mater Interfaces 2019, 11, 940; (b) J.
Lyu, X. Zhang, K. I. Otake, X. Wang, P. Li, Z. Li, Z.
Chen, Y. Zhang, M. C. Wasson, Y. Yang, P. Bai, X. Guo,
T. Islamoglu and O. K. Farha, Chem. Sci. 2019, 10, 1186.
(c)
1
2
3
4
5
Runs
Fig. 6 PXRD patterns of as-synthesized 1 and after
three and five catalytic runs (a), the leaching test (b)
and recycling test (c) for the reactions of
hydrosilylation of alkynes.
4 (a) X. L. Zhang, S. M. Li, S. Chen, F. Feng, J. Q. Bai
and J. R. Li, Ecotoxicol. Environ. Saf. 2020, 187, 109821;
(b) M. H. Zhang, K. Gu, X. W. Huang and Y. F. Chen,
Phys. Chem. Chem. Phys. 2019, 21, 19226; (c) J. P. Zhang,
H. L. Zhou, D. D. Zhou, P. Q. Liao and X. M. Chen,
Natl. Sci. Rev. 2018, 5, 907.
Conclusions
In this paper, we synthesized a pair of enantiomers
Co-MOF of 1/2. On account of the chemical stability
and open metal sites in this framework, the
5 (a) J. Zhang, J. Chen, S. Peng, S. Peng, Z. Zhang, Y.
Tong, P. W. Miller and X. P. Yan, Chem. Soc. Rev. 2019,
48, 2566; (b) M. S. Yao, J. W. Xiu, Q. Q. Huang, W. H.
Li, W. W. Wu, A. Q. Wu, L. A. Cao, W. H. Deng, G. E.
Wang and G. Xu, Angew. Chem., Int. Ed. 2019, 58, 14915;
(c) C. Xu, Y. Pan, G. Wan, H. Liu, L. Wang, H. Zhou, S.
H. Yu and H. L. Jiang, J. Am. Chem. Soc. 2019, 141, 19110.
heterogeneous
catalytic
performanced
good
recoverability and shown not only in the sequential
one-pot azide-alkynes cycloaddition and Friedel-
Crafts reactions of indoles with trans-β-nitrostyrenes,
but also in the hydrosilylation of alkynes reactions
under a relatively mild condition. Besides, the
corresponding catalytic mechanism was revealed.
6 (a) L. J. Small, R. C. Hill, J. L. Krumhansl, M. E.
Schindelholz, Z. Chen, K. W. Chapman, X. Zhang, S.
Yang, M. Schroder and T. M. Nenoff, Appl. Mater.
Interfaces. 2019, 11, 27982; (b) S. Shyshkanov, T. N.
guyen, A. Chidambaram, K. C. Stylianou and P. J.
Dyson, Chem. Commun. 2019, 55, 10964; (c) Q. Liu, Y.
Song, Y. Ma, Y. Zhou, H. Cong, C. Wang, J. Wu, G. Hu,
M. O'Keeffe and H. Deng, J. Am. Chem. Soc. 2019, 141,
488.
Conflicts of interest
The authors declare no conflict of interest.
Acknowledgements
Thank the National Natural Science Foundation of
China (Grants 21861005 and 21461003), Guangxi
7 (a)Z. Zhang, L. Bai and X. Hu, Chem. Sci. 2019, 10,
3791; (b) S. K. Das, S. Chatterjee, S. Bhunia, A. Mondal,
P. Mitra, V. Kumari, A. Pradhan, A. Bhaumik, Dalton
Trans. 2017, 46 (40), 13783-13792; (c) G. Gumilar, Y. V.
Kaneti, J. Henzie, S. Chatterjee, J. Na, B. Yuliarto, N.
Nugraha, A. Patah, A. Bhaumik, Y. Yamauchi,
Chemical Science 2020, 11 (14), 3644-3655; (d)C. Tan.;
K. Yang.; J. Dong. Y. Liu. Y. Liu. J. Jiang. Y. Cui, J Am
Chem Soc 2019, 141 (44), 17685-17695; (e) Q. Yang.; Q.
Xu. H. L ， Jiang, Chem Soc Rev 2017, 46 (15), 4774-
4808.
Natural
Science
Foundation
(Grants
2016GXNSFFA380010 and 2018GXNSFBA281151), and
Foundation of Key Laboratory for Chemistry and
Molecular Engineering of Medicinal Resources (Grants
CMEMR2018-C15) for funding this research.
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ARTICLE
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DOI: 10.1039/D0NJ04626D
A Robust Heterogeneous Co-MOFs Catalyst in Azide-alkynes
Cycloaddition and Friedel-Crafts Reactions as well as
Hydrosilylation of Alkynes†
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Tai-Xue Wu,a‡ Jun-Song Jia,a‡ Wei Luo,a He-Dong Bian,ab* Hai-Tao Tang,a*
Ying-Ming Pan,a Fu-Ping Huanga*
A robust Co(II) MOFs with high stability in high temperature,
different solvent and strong acid/base condition, were gram-scale
prepared to be an effective heterogeneous catalyst to promote
azide-alkynes cycloaddition reaction, Friedel-Crafts reactions of indoles
and hydrosilylation of alkynes reactions.