Synthesis, structure and multifunctional catalytic properties of a Cu(i)-coordination polymer with outer-hanging CuBr2

Article abstract of DOI:10.1039/c6ra20767g

A 1D Cu(i)-coordination polymer [(CuL1)(CuBr₂), 1] carrying external copper bromide moieties was synthesized. The outer-hanging [CuBr₂]^- moiety is attached to the 1D Cu(i)-CP backbone via a Cu?Cu bonding interaction, which makes it look like a coordination polymer supported CuBr₂ species. 1 exhibits excellent multifunctional catalytic activity for phenol acetylation, A³-coupling (aldehyde-alkyne-amine) and styrene oxide methanolysis reactions. Its heterogeneous catalytic nature was confirmed by solution leaching experiment and it can be reused without significant loss of its catalytic activity and selectivity for the above reactions.

Full text of DOI:10.1039/c6ra20767g

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Synthesis, structure and multifunctional catalytic properties of
Cu(I)-coordination polymer with outer-hanging CuBr2
Received 00th January 20xx,
Accepted 00th January 20xx
NengꢀXiu Zhu,† ChaoꢀWei Zhao,† Jing Yang, XueꢀRu Wang, JianꢀPing Ma and YuꢀBin Dong*
A 1D Cu(I)ꢀcoordination polymer ([(CuL1)(CuBr2), 1] carrying external copper bromide moiety was synthesized. The
outerꢀhanging [CuBr2]ꢀ moiety is attached to 1D Cu(I)ꢀCP backbone via Cu⋅⋅⋅Cu bonding interaction, which makes it look
like coordination polymer supported CuBr2 species. 1 exhibits excellent multifunctional catalytic activity for phenol
acetylation, A3ꢀcoupling (aldehydeꢀalkyneꢀamine) and styrene oxide methanolysis reactions. Its heterogeneous
catalytic nature was confirmed by solution leaching experiment and it can be reusable without significant loss its catalytic
activity and selectivity for above reactions.
DOI: 10.1039/x0xx00000x
www.rsc.org/
such as multiꢀstep pharmaceutical synthesis and food or
cosmetic industries. For example, phenol acetylation is widely
used as protecting group in multiꢀstep pharmaceutical synthesis
Introduction
Coordination polymers (CPs) are hybrid polymeric complexes
with infinite network structures composed of organic ligands
and metal ions. As an attractive class of hybrid solid materials,
CPs received considerable attention because of their fascinating
physical and chemical properties.1 Among various CPs, Cu(I)
halidesꢀbased CPs have been widely explored due to their
interesting structural feature and possible applications in
luminescenceꢀbased sensors, solar system, and biological
probes.2
and food or cosmetic industries.6 In this procedure, organic
phosphine and inorganic metal triflate complexes are often used
as the catalysts.7 As for A3ꢀcoupling (aldehydeꢀalkyneꢀamine)
reaction, which is a typical oneꢀpot multiꢀcomponent coupling
reaction, the resulted propargylamines are the important
intermediates for synthesis of various nitrogenꢀcontaining
biologically active compounds.8 The precious metal complexes,
including Au, Ag, Ir and Ruꢀcompounds,9 are often selected to
facilitate these multicomponent coupling reactions. In addition,
ringꢀopening of epoxides with nucleophilic regents is an
important path to access to compounds with versatile 1, 2 type
It is well known that noble metals such as Pd, Rh and Ru are
valuable species to catalyse CꢀC, CꢀO and CꢀN bond formation,
but usually with the assistance of toxic organic phosphorus
ligands. It is similar to these soft metal Lewis acids, Cu(I) can
easily form adducts with a wide range of organic donors such
as amine, Nꢀcontaining heterocycles, organic nitriles and so
on,3 and their Cu(I) complexes have long been employed in
organic synthesis as catalysts via metalꢀcomplexed
intermediates such as πꢀcopper complexes.4 On the other hand,
copper has been demonstrated to be not ecoꢀfriendly and is an
important nonpoint source pollutant in aquatic ecosystems
worldwide.5 So the development of new type of ecoꢀfriendly
heterogeneous cheaper Cu(I) CPsꢀbased catalysts is a topic of
great interest.
functional groups, including
βꢀalkoxyalcohols. So far, many
molecular metal complexes such as In(III), Sn(II, IV), Cr(II,
III), Al(III), Co(III) and Cu(II)ꢀcomplexes10 are used as the
catalysts to epoxide methanolysis.
As shown above, most of these homogeneous catalyst systems
for these three types of reactions cannot be reusable and suffer
from the loss of the hazardous or precious catalysts at the end
of the reactions. For achieving more ecoꢀfriendly catalysts and
minimizing environmental pollution, the construction of CPsꢀ
based heterogeneous catalysts is highly demanded.
In this contribution, we report a new 1D Cu(I)ꢀCP which is
generated from CuBr2 and the fluoreneꢀbridged imidazoleꢀ
Phenol acetylation, styrene oxide methanolysis, and A3ꢀ
coupling (aldehydeꢀalkyneꢀamine) reactions are three important
types of reactions and frequently used in synthetic chemistry
capped ligand
reactions. Interestingly,
L
with methyl side chain under solvothermal
contain [CuBr2]ꢀ species as the
1
counter ions instead of simple bromide anion. Furthermore, it,
as an external counter anion, attached to the chain backbone via
Cu⋅⋅⋅Cu bonding interaction, which is rarely observed in CPs. In
addition,
1 can be a highly heterogeneous catalyst to promote
phenol acetylation, A3ꢀcoupling (aldehydeꢀalkyneꢀamine) and
styrene oxide methanolysis reactions under mild conditions.
Experimental
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Materials and methods
bond length and angle parameter are listed in Tables S4ꢀS5
(ESI).
Catalytic reaction
Phenol acetylation. Acetic anhydride (4 mmol) was added to a
All chemicals and solvents were at least of analytic grade and
employed as received without further purification. The Infrared
(IR) spectra were recorded from dry KBr pellets in the 400ꢀ
4000cmꢀ1 range on a PerkinElmer 1600 FTIR spectrometer. The
CH2Cl2 (1 mL) solution of
After addition of (5 % mol), the mixture was stirred at room
temperature for 2 h (monitored by TLC, petroleum/CH2Cl2 = 1 :
1). was recovered by centrifugation, washed with MeOH and
dried at 80
pꢀbromophenol (173 mg, 1 mmol).
1
C,
H and N elemental analysis were conducted on a
PerkinElmer Model 2400 analyzer. Solution phase 1H NMR
and 13C spectra were obtained on an AMꢀ300 spectrometer.
1
°
C.
Chemical shifts are reported in
δ units relative to TMS. Powder
A3-coupling (aldehyde-alkyne-amine) reaction. A mixture of
phenylacetylene (120 mg, 1.2 mmol), paraformaldehyde (PFA,
Xꢀray diffraction (PXRD) measurements were performed at
293K on a D8 ADVANCE diffractometer (Cu K
1.5406Å). GCꢀMS analysis was performed on
α
a
, λ =
J&K
30 mg, 1.0 mmol), piperidine (94 mg, 1.1 mmol) and
1 (5 %
mol) was stirred at room temperature in nitrogen atmosphere
for 6 h (monitored by TLC). After addition of ether, the product
was purified by column chromatography on silica gel
S011525−300 gas chromatographic (Agilent 6890GCꢀ
5973MS). XPS spectrum was obtained from THI5300 (PE).
ESIꢀMS spectra were obtained on Thermo LCQꢀFleet machine.
(hexane/ethyl acetate
centrifugation and washed with ether and MeOH and dried at
80 C.
= 3 : 1). 1 was recovered by
Synthesis of [(CuL1)(CuBr2)] (1)
L1 (5.2 mg, 0.016 mmol), CuBr2 (11 mg, 0.05 mmol), water
(2 mL) and THF (0.22 mL) was sealed in a glass tube (6 mL).
The mixture was heated at 150°C for 72 h and cooled slowly to
°
Styrene oxide methanolysis. A methanol (5 mL) solution of
styrene oxide (1 mmol) and catalyst (0.02 mmol, 2 mol %) was
stirred at 50°C for 7 hours. The reaction was monitored by
TLC. The conversion and selectivity were determined by GCꢀ
MS and HPLC. The product was further confirmed by 1H
NMR. After each catalytic run, the catalyst was recovered by
centrifugation and washed by fresh methanol. After dried at
70°C for 1 hour, the catalyst was used in the next catalytic run.
XRPD patterns of the recovered catalyst indicated the structure
integrity of the CPs were maintained.
room temperature over a period of 50 h. Yellow crystals of
1
were obtained. Yield: 61% (based on L1). IR (KBr pellet, cmꢀ
1): 3459(w), 3124(m), 2960(w), 1613(w), 1513(s), 1445(w),
1308(s), 1255(m), 1151(w), 1064(m), 958(w), 831(m), 737(w),
647(w). Anal. Calcd for C21H18BrCuN4: C 53.68, H 3.86, N
11.92. Found: C 53.96, H 3.79, N 11.41. ESIꢀMS (DMSO) for
[Cu2Br2]+: m/z = 284.5 (11), 286.3 (73), 288.5 (100), 290.6 (31),
292.6 (33). ESIꢀMS (DMSO) for [Cu2L1]+: m/z = 453.5 (100),
454.3 (16), 455.3 (39), 456.4 (17).
Synthesis of [(CuL2)2(Cu2Br4)] (2)
Leaching test
L2 (5.6 mg, 0.016 mmol), CuBr2 (11 mg, 0.05 mmol), water
(2 mL) and THF (0.22 mL) was sealed in a 6 mL glass tube.
The mixture was heated at 150°C for 72 h and cooled slowly to
Solid catalyst of
by filtration during the reaction process. The reaction was
continued with the filtrate in the absence of . No further
1 was separated from the reaction solution
1
room temperature over a period of 50 h. Yellow crystals of
2
were obtained. Yield: 59% (based on L2). IR (KBr pellet, cmꢀ
1): 3445(w), 3120(w), 2926(w), 1614(w), 1509(s), 1470(w),
1304(w), 1251(w), 1107(w), 1063(m), 811(w), 732(w), 651(w).
Anal. Calcd for C23H22BrCuN4: C 55.48, H 4.45, N 11.25.
Found: C 55.26, H 4.71, N 11.53.
increase in either conversion or selectivity of the product was
detected, which confirms that the catalytically active sites for
phenol acetylation, A3ꢀcoupling (aldehydeꢀalkyneꢀamine) and
styrene oxide methanolysis reactions located on 1.
Results and discussion
X-ray crystallography
Singleꢀcrystal Xꢀray diffraction data of
Agilent Technologies SuperNova diffractometer with graphite
monochromated Mo Kα radiation ( = 0.71073 Å) and Cu Kα
radiation ( = 1.54184 Å), respectively. Data corrections for
incident and diffracted beam absorption effects were done with
CrysAlisPro software. Singleꢀcrystal Xꢀray diffraction data of
were measured on a Bruker SMART APEX CCDꢀbased
diffractometer (Mo K radiation, = 0.71073 Å). The raw
1 was measured on an
λ
λ
2
α
λ
Scheme 1. Synthesis of L1 and 1. The photograph of ground 1 is inserted.
frame data were integrated into SHELXꢀformat reflection files
and corrected for Lorentz and polarization effects using
SAINT.11 Corrections for incident and diffracted beam
absorption effects were applied using SADABS.11 None of the
crystals showed evidence of crystal decay during the process of
Synthesis and structural analysis
As shown in Scheme 1, was synthesized by heating the DMF
solution of imidazole and corresponding 2,7ꢀbromide
substituted fluorines (120°C for 8 hours) in the presence of
L
data collection. The structures of
1ꢀ2 were solved by direct
Cs2CO3 and CuI in satisfied yields (76 %, ESI). Compound
was obtained as yellow crystalline solids by the combination of
CuBr2 and in a mixedꢀsolvent system of MeOH/THF at
150°C for 72 h in moderate yields (61 %).
1
methods with SHELXS program and refined by full matrix
leastꢀsquares technique on F2 including all reflections using the
SHELXLꢀ97 program package.11 The crystal data and
refinement parameters are summarized in Table 1, and selected
L
2 | J. Name., 2012, 00, 1-3
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The structure of
1
was resolved through Xꢀray singleꢀcrystal direction. Interestingly, the [CuBr2]ꢀ cuprate ions are adhered to
diffraction analyses. The pure phase of the obtained yellow the chain backbone by weak Cu⋅⋅⋅Cu interaction with a
crystals was confirmed by XRPD (ESI). It is noteworthy to Cu(1)⋅⋅⋅Cu(2) bond length of 2.8717(8) Å.
point out that the copper ions in
reduction of Cu(II) to Cu(I) by
1
is univalent (ESI). The in situ
Table 1. Crystal Data and Structural Refinement Parameters for 1 and 2.
N
ꢀheterocycle containing
ligands, especially under hydro/solvothermal conditions, is
1
2
quite common, with a series of reports having appearing in the
formula
C21H18Br2Cu2N4
613.29
C23H22Br2Cu2N4
641.35
literature for Cu(SO3CF3)2,12a Cu(NO3)2,12bꢀd CuSO4
and
fw
12e
12f
λ/Å
0.71073
monoclinic
P21/c
0.71073
Triclinic
P-1
CuCl2 salts. Notably,
1 is stable in common organic solvent
crystal system
systems such as toluene, CHCl3, THF, cyclohexane, CH3CN
and acetone (ESI), which will allow it to be used as
heterogeneous catalyst in various organic solvents.
space group
T/K
100.01(10)
12.9017(3)
17.3862(5)
9.3722(2)
90.00
298(2)
a (Å)
10.749(3)
10.987(3)
11.774(3)
68.908(4)
64.794(4)
76.046(4)
1167.5(5)
2
b (Å)
c (Å)
α (deg)
β (deg)
100.322(3)
90.00
γ (deg)
V (Å3)
2068.27(9)
4
Z
ρcak/g·cm-3
μ/ mm-1
1.970
1.824
5.936
5.262
F (000)
1200
632
GOF
1.033
0.783
Data/restraints/parameters
R1 [I>2σ(I)]
3874/0/264
0.0383
4103/36/310
0.0513
wR2[all data]
0.0928
0.1014
The crystal packing (Fig. 1, viewed down the chain direction)
shows that the [CuBr2]ꢀ anions are located at both sides of the
chains, and the interchain Cu⋅⋅⋅Cu distances are 7.6 and 7.7 Å,
respectively.
1 herein is a rare example of a complex containing
an unsupported Cu(I)⋅⋅⋅Cu(I) interaction, with a short distance
similar to that of [CuL]+[CuCl2]ꢀ (L
=
1, 1’ꢀbis(2ꢀ
pyridyl)octamethylferrocenene species (dCu(I)
= 2.810(2)
⋅⋅⋅Cu(I)
Å).14 Such close contact may be interpreted in terms of a weak
bonding interaction between the two d10 metal atoms.
Fig. 1 a) The zigzag chain of
1 was shown. The asymmetric unit was selected in
the purple oval. Linear [CuBr2]- were adhered to Cu(I) centre on the chain
backbone as balanced ions through weak Cu⋅⋅⋅Cu interactions. Hydrogen atoms
As shown above, the structural feature of
1 is interesting. First,
were omitted for clarity. b) Crystal packing of 1. c) Side view of 1. Polymer back
bone is shown in space-filling model.
the 1D CP chain contains univalent copper nodes which are in
lowꢀcoordination environment. Second, the [CuBr2]ꢀ moiety
instead of simple halide ion serves as the counter anion,
furthermore, attached to the chain backbone via weak Cu⋅⋅⋅Cu
Single crystal Xꢀray diffraction analysis (Table 1) revealed
that crystallizes in the monoclinic P21/c space group. As
shown in Fig. 1, there are two kinds of crystallographic
independent Cu(I) ions. The Cu(1) atoms on the ionic chain
backbone adopt an approximate linear coordination
environment which is consisting of two nitrogen atoms from
1
binding interaction. As shown in Fig. 1,
1 herein could be
considered as a CPsꢀsupported CuBr2 composite material. Such
material would be good catalyst candidate for those organic
transformations usually promoted by Lewis acid type inorganic
catalysts.
two L1 (∠N(1)–Cu(1)–N(4) = 169.82(17)°). The Cu(1)–N(1)
and Cu(1)–N(4) bond lengths are 1.885(3) and 1.884(3) Å
respectively. The other Cu(2) ion, together with two Brꢀ, forms
the [CuBr2]ꢀ counter ion. The [CuBr2]ꢀ moiety is nearly linear
Catalytic property
Phenol acetylation.
(∠Br(1)–Cu(2)–Br(2) = 174.50(4)°) and symmetrical (Cu(2)–
Br(1) and Cu(2)–Br(2) bond lengths are 2.2345(8) and 2.2292(8)
Å respectively). These distances are slightly longer than
average value of 2.216 Å for another twelve examples of linear
[CuBr2]ꢀ anions reported in the Cambridge Structural
Database.13 In the solid state, the Cu(1) nodes are connected to
each other by the bidentate bent L1 ligands to generate a zigzag
polymer chain extended along the crystallographic [101]
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Journal Name
Entry
substrate
T (h)
Conversion (%)b
Selectivity (%)b
>99.00
Br
I
OH
OH
1
2
2
6
>99.00
>99.00
>99.00
H3C
O2N
OH
OH
3
4
5
12
3
>99.00
>99.00
>99.00
>99.00
>99.00
>99.00
H3CO
OH
OH
7
6
15
>99.00
>99.00
a Reaction conditions: r.t., 1 (5 mol %), CH2Cl2, 2-15 h. b isolated yields.
Fig. 2 1-catalyzed 4-bromophenol acetylation: a) 1H NMR (300 MHz, CDCl3)
spectrum of the acetylation product. b) Reaction time examination and leaching
test. c) Recycling catalytic test.
Then, we converted a variety of substituted phenol substrates
into corresponding aryl acetates to further explore the scope of
this 1ꢀcatalysed procedure, as summarized in Table 2. Electronꢀ
Phenol acetylation is generally catalysed by inorganic metal
salts or substrateꢀsupported inorganic composite materials. To
our knowledge, only one phenol acetylation example which is
withdrawing groups attached substituted phenols (entries 1, 2
and 4) were converted to the corresponding aryl acetates in
yields. On the other hand, acetylated yields of the electronꢀ
donating groups containing substrates (entries 3 and 5) are also
quantitative, but they took much longer time. In addition, the
acetylation of bulky 2ꢀnaphthol was also performed, it was
found to be acetylated even slower than those electron rich
groups, which might be resulted from the sterically blocking
catalysed by CPs (Zn/Cd CPs) was reported.15
1 carrying
external CuBr2 herein can be considered as a Cu(I) CPꢀ
supported CuBr2 Lewis acid species, in which the CuBr2 unit is
stabilized by the weak Cu⋅⋅⋅Cu bonding interaction. Based on
the unique structural feature,
1 was expected to be the catalyst
for phenol acetylation which us usually catalysed by the Lewis
acids.
In a typical experiment, 4ꢀbromophenol was treated with
effect. The XRPD patterns of
1 and that after being used for
five catalytic runs showed that the structural integrity of
wellꢀpreserved (ESI).
1 was
acetic anhydride (4 equiv) in the presence of finely ground
1 (5
A3-coupling (aldehyde-alkyne-amine) reaction.
mol %) in CH2Cl2 (1 mL) at room temperature for 2 h
(monitored by TLC, petroleum ether/CH2Cl2 = 1 : 1), the
acetylation product was isolated as white solid in quantitative
yield (>99.00 %) and its structure was confirmed by the 1H
In addition, inorganic copper complexes are known to be good
catalysts for A3ꢀcoupling (aldehydeꢀalkyneꢀamine) reaction.16
Inspired by this,
1 was also used to test its catalytic activity for
A3ꢀcoupling reaction.
NMR spectrum (Fig. 2) The catalyst of
centrifugalization. After washed with anhydrous MeOH and
dried at 80 C for 2 h, it was reused in the next catalytic cycle.
1 can be recovered by
For ecoꢀfriendly synthesis requirement, the A3ꢀcoupling
reaction was carried out under solventꢀfree condition. A
mixture of phenylacetylene (120 mg, 1.2 mmol),
paraformaldehyde (30 mg, 1.0 mmol) and piperidine (94 mg,
°
The catalyst amount used herein for this acetylation was
determined by a series of parallel experiments. With the
successive increase in the amount of 1, (1, 2, 3, 4 and 5 mol %,
respectively), the reaction time for the complete 4ꢀbromophenol
acetylation significantly decreased (11, 7, 4.5, 3 and 2 h,
1.1 mmol) in the presence of finely ground
1 (30.6 mg, 5 mol %)
was stirred at room temperature for 6 h (monitored by TLC) to
afford crude product. The product was purified by column on
silica gel (nꢀhexane/ethyl acetate = 3 : 1). The catalyst of
recovered by the centrifugation. After washed with ether and
dried at 80 C for 2 h, was reused for next run.
1 was
respectively).
1 performed as a heterogeneous catalyst in the
phenol acetylation, which was confirmed by the leaching test.
As shown in Fig. 2, no further reaction occurred in the absence
°
1
The reaction was investigated at room temperature for a
different period of time. No improved yield was observed by
extending the reaction time from 6 h (93.8 %) to 12 h (94.1 %).
of
1
after ignition of the acetylation at 1 h. In addition, Fig. 2
can be reused and the quantitative yield for 4ꢀ
shows that
1
bromophenyl acetate was obtained within the five recycling
runs. The corresponding reaction catalysed by reported Zn/Cd
CPs afforded 99 % yield under room temperature for 20/40 h
using CH2Cl2 as solvent.15
In addition, when using a smaller amount of 1, for example, 1,
2, 3 and 4 % mol, the threeꢀcomponent coupling yield reduced
to 56.4, 67.9, 78.3, 81.6 %, respectively. Thus, the optimized
reaction conditions for A3ꢀcoupling are
1
(5 mol %) in the
absence of an organic solvent at room temperature (Fig. 3). It is
similar to phenol acetylation, is stable during the recycling
1
reaction (ESI) and can be reused for five times without loss of
its catalytic activity, and the yields lie in a range of 91.4ꢀ93.8 %
(Fig. 3).
Table 2. Acetylation of the phenols with different substituted groups catalysed by 1.a
4 | J. Name., 2012, 00, 1-3
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Cu/PMAꢀMILꢀ101(Cr)17a and Cu(II)ꢀMOF17b are able to
promote this threeꢀcomponent coupling in 99 (21 h, 40 C, 1,4ꢀ
dioxane), 60 (17 h, 40 C, 1,4ꢀdioxane) and 95 % (12 h, 45 C,
CH2Cl2) yields, respectively. Compared to the reported CPsꢀ
°
°
°
catalysts,
1 (r.t., solventꢀfree, 94 %) herein can be a valuable
complement for the CPs to heterogeneous A3ꢀcoupling catalysts.
Styrene oxide methanolysis
In organic synthesis, epoxides are invaluable building blocks for
introduction of diverse functionalities in a hydrocarbon backbone
in a 1, 2ꢀfashion. To get high regioselectivity of the epoxide ringꢀ
opening reaction toward the expected product, mild conditions,
effective and ecoꢀfriendly catalysts have to be used. The past few
years have witnessed a rapid increase in the number of reports on
the use of CPs in organic synthesis, including epoxide ringꢀ
opening reaction, due to their heterogeneous nature. As indicated
in Table 4, a series of CPs have been chosen for alcoholysis of
epoxides. The results indicate that these metalꢀorganic polymeric
coordination materials exhibit the similar catalytic activity to
those inorganic complexes such as metal halides and metal
carboxylates.
Fig. 3 1-catalyzed A3-coupling (phenylacetylene-piperidine-paraformaldehyde): a)
1H NMR (300 MHz, DMSO-d6) spectrum of the coupling product. b) Reaction time
examination and leaching test. c) Recycling catalytic test.
Table 3
.
A3ꢀcoupling (aldehydeꢀalkyneꢀamine) reaction catalysed by 1 a
.
Entry
Alkyne
Aldehyde
(CH2O)n
CHO
Amine
Yield (%)a
94
Table 4. Ring opening of styrene oxide with methanol catalysed by CPs.
1
2
HN
HN
HN
86
3
4
5
6
7
8
CHO
(CH2O)n
(CH2O)n
90
93
89
91
88
93
Entry
Cat.
Cond.
Conv. (%)a
Ref.
HN
N
1
2
Cu(bpy)(H2O)2(BF4)2(bpy)
[Fe (BTC)]
3 h, r.t.
1 h, 40°C
0.1 h, r. t.
3 days, r.t.
9 h, 50°C
2.5 h, 40°C
24 h, 55°C
1 h, 55°C
48 h, 55°C
2 h, 35°C
110 h, 60°C
12 h, r.t.
99
93
18
19
HN
HN
HN
HN
O
3
MIL-101-SO3H
99
20
4
Cu(II)-CPs
99
21
(CH2O)n
(CH2O)n
(CH2O)n
H3C
H3CO
Cl
5
Co(II)-BTT
67
22
6
Cu3(BTC)2
90
23
7
[La2(H3bmt)2(H2O)2].H2O
La(H4bmt)(H5bmt)(H2O)2
[Eu(Hpmd)(H2O)]
[La2(H3nmp)2(H2O)4]4.5H2O
TMU-18, TMU-19
Cu(II)-CPs
80
24
8
100
100
100
100
100
62
25
9
26
10
11
12
13
14
15
16
27
28
a reaction conditions: r. t., 1 (5 mol %), solvent-free, 6 h.
29
MIL-100(Fe)
24 h, 40°C
1 h, 40°C
2 h, r.t.
30
To test the scope of this
1
catalysed A3ꢀcoupling reaction, we
[La(H3nmp)]-MOF
Cu(II)-MOF
100
93
31
extended the studies to different combinations of alkynes,
aldehydes and amines under the optimal reaction conditions.
The results are summarized in Table 3. Compared to
phenylacetylene/piperidine/isobutyraldehyde (entry 2), the
32
Ln(III)-MOF
29 h, 55°C
80
33
This
work
17
1
7 h, 50°C
97
combination
of
phenylacetylene,
piperidine
with
paraformaldehyde (entry 1) or cyclohexanecarboxaldehyde
(entry 3) gave the better isolated yields. For the azaꢀ (entry 4)
and
oxaꢀpiperidine
(entry
5)
with
phenylacetylene/paraformaldehyde, the isolated yields are still
high, 89ꢀ93 %. On the other hand, aromatic alkynes with both
electronꢀdonating (entries 6 and 7) and electronꢀwithdrawing
groups (entry 8) for this threeꢀcomponent coupling afforded the
corresponding propargylamines in good to excellent yields.
So far, there are three examples related to phenylacetyleneꢀ
piperidineꢀparaformaldehyde A3ꢀcoupling reaction catalysed by
CPs. Cu(2ꢀpymo)2 (2ꢀpymo = 2ꢀhydroxypyrimidinolate),16a
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Table 5. Methanolysis of styrene oxide and extended substrates catalysed by 1.a
Entry
1
Substrate
T (h)
7
Conv. (%) b
97
Select. (%) b
O
>99
O
2
3
4
Cl
F
24
24
24
77
80
82
>99
>99
>99
O
Fig. 4 1-catalyzed styrene oxide methanolysis: a) 1H NMR (300 MHz, CDCl3)
spectrum of the coupling product. b) Reaction time examination and leaching
test. c) Recycling catalytic test.
O
O
5
O
24
67
>99
In a typical catalytic experiment, the reaction was performed
with 1 mmol of styrene oxide in the presence of 2 mol % of
a Reaction conditions: 1 (2 mol %), MeOH, 50°C, 7-24 h. b determined by GC.
finely ground
methanol (5 mL). The reaction was monitored by TLC and the
reaction was finished in 7 h. The obtained product is ꢀalkoxy above phenol acetylation, styrene oxide methanolysis and
substituted alcohol (yield of 97 % with 99 % selectivity), aldehydeꢀalkyneꢀamine three component coupling reaction, the
which was further confirmed by H NMR spectrum (Fig. 4). In XPS and ICP measurements (ESI) were performed on after
order to gain insight into heterogeneous nature of , leaching the catalytic reactions, respectively. The results strongly
test was carried out. As indicated in Fig. 4, no further reaction evidenced that no valence state change occurred for Cu and Br
took place without after initiation of the alcoholysis reaction after catalysis and basically no copper and bromine species
at 1.5 h. This finding suggests that the reaction likely proceeded leaching was observed after the catalytic reactions, which
on the heterogeneous surface. As a heterogeneous catalyst, further support is an ideal heterogeneous catalyst herein.
can be reused. After each catalytic cycle, could be easily We assume that the exposed CuBr2 moiety in serves as the
recovered by centrifugation and filtration, and then washed by main active catalytic sites. For confirming this, we synthesized
fresh methanol. After dried at 80°C for 2 h, the catalyst was a Cu(I)ꢀCP ( ), which contains the embedded type of CuBr
1. The reaction was performed at 50°C in
To further confirm
1 is a typical heterogeneous catalyst for
β
>
1
1
1
1
1
1
1
1
2
directly used in the next run.
moiety, based on fluoreneꢀbridged imidazoleꢀcapped ligand L2
As indicated in Fig. 4, after seven consecutive catalytic runs,
1
with ethyl side chain under the same solvothermal conditions as
was demonstrated to be highly crystalline based on XRPD that of
patterns and the XRPD patterns of recovered catalyst indicated crystallizes in the triclinic P-1 space group (Table 1). As
the structure integrity of was well maintained (ESI). Fig. 4 shown in Fig. 5, here are two kinds of crystallographic
shows that the catalytic activity of can be used up to seven independent Cu(I) centres in . The Cu(1) centre on the chain
1 (Fig. 5).
2
1
t
1
2
catalytic runs without significant activity loss, and the high lies in a triangular coordination environment, a typical
selectivity toward 2ꢀmethoxyꢀ2ꢀphenylethanol product is well
maintained. As shown in Table 4, the reported conversion of
CPsꢀcatalysed styrene oxide methanolysis lies in a range of 62 ꢀ
100 %, and the reaction temperature and time are in the range
of r.t. ꢀ 60°C and 0.1 h ꢀ 3 days, respectively. 1 (7 h, 50°C,
97 %) is a competitive new member in the catalyst CPs family
for styrene oxide methanolysis.
When the substrates extended from styrene oxide to substituted
styrene oxide and 1, 2ꢀcyclohexene oxide (Table 5), the
conversions are reduced to 67ꢀ82 % (entries 2ꢀ5), moreover, took
much longer time. For example, only ca. 20 and 50
%
conversions for the extended epoxide substrates were observed
when these reactions proceeded at 7 and 15 h.
Fig. 5 a) Synthesis of 2. The photograph of ground 2 is inserted. b) The ladder
chain in 2 is shown. The asymmetric unit is depicted in the purple oval. Hydrogen
atoms were omitted for clarity.
coordination fashion for Cu(I) ion, composed of two Nimidazol
atoms and one Brꢀ. The Cu(1)–N(1), Cu(1)–N(4) and Cu(1)–
Br(1) bond lengths are 1.89(3), 1.93(2) and 2.7581(14) Å,
6 | J. Name., 2012, 00, 1-3
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respectively. The sum of three angles around Cu(1) centre are
357.64°( N(1)–Cu(1)–N(4) = 157.7(10)°, N(1)–Cu(1)–Br(1)
= 98.64(17)°, N(4)–Cu(1)–Br(1) = 101.3(9)°) indicating
three coordinating atoms are basically coplanar. It is different
from features 1D double zigzag chain motif and the
[Cu2Br4]2ꢀ counter ions are located between chains and bridge
two neighbouring single chains via Cu(1)ꢀBr(1) linkage
(2.7581(14) Å). The [Cu2Br4]2ꢀ cluster core is a planar divalent
anion. The bridging CuꢀBr distances (dCu(2)–Br(2) = 2.4171(14)
and dCu(2)–Br(2)#1) = 2.4034(16) Å) are longer than for the
terminal CuꢀBr bond length (dCu(2)–Br(1) = 2.3258(15) Å). In
Acknowledgements
∠
∠
We are grateful for financial support from NSFC (Grant Nos.
21671122, 21475078 and 21271120), 973 Program (Grant Nos.
2013CB933800) and the Taishan Scholar’s Construction
Project.
∠
1, 2
Notes and references
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°
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>
2
p
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interaction as an outerꢀhanging species to generate a CPꢀ
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For table content
A CuBr2 species attached 1D Cu(I) coordination polymer can be a highly effective multifunctional heterogeneous catalyst to promote
phenol acetylation, A3ꢀcoupling (aldehydeꢀalkyneꢀamine) and styrene oxide methanolysis reactions, respectively.
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