An aluminum(III) picket fence phthalocyanine-based heterogeneous catalyst for ring-expansion carbonylation of epoxides

Article abstract of DOI:10.1039/c8ta11877a

An effective heterogeneous catalyst for ring-expansion carbonylation of epoxides may have additional advantages over the homogeneous counterpart in terms of facile product separation and recyclability. A new Al(iii) picket fence phthalocyanine complex was synthesized and directly knitted using the Friedel-Crafts reaction to prepare a solid porous network, which was ultimately used to immobilize [Co(CO)₄]^- ions. The resulting heterogeneous catalyst, [Lewis acid]⁺[Co(CO)₄]^-, efficiently catalyzes the conversion of various epoxides into the corresponding β-lactones with high selectivity (99%) and stoichiometric conversion under mild reaction conditions, along with good functional group tolerance.

Full text of DOI:10.1039/c8ta11877a

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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
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DOI: 10.1039/C8TA11877A
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An
aluminum(III)
picket
fence
phthalocyanine-based
heterogeneous catalyst for ring-expansion carbonylation of
epoxides
Received 00th January 20xx,
Accepted 00th January 20xx
Jianwei Jianga and Sungho Yoona*
DOI: 10.1039/x0xx00000x
www.rsc.org/
An effective heterogeneous catalyst for ring-expansion carbonylation of epoxides may have additional advantages over the
homogeneous counterpart in terms of facile product separation and recyclability. A new Al(III) picket fence phthalocyanine
complex was synthesized and directly knitted using the Friedel-Crafts reaction to prepare solid porous network, which was
untimatly used to immobilize [Co(CO)4]- ions. The resulting heterogeneous catalyst, [Lewis acid]+[Co(CO)4]-, efficiently
catalyzes the conversion of various expoxides into corresponding β-lactones with high selectivity (99%) and stoichiometric
conversion under mild reaction conditions, along with good functional group tolerance.
LA
[LA]+[Co(CO)4]-
O
CO
O
O
Co(CO)4
LA+
O
Introduction
LA
O
A
B
pathway
Co(CO)4
R
O
+
R
[LA]+[Co(CO)4]-
LA
O
β-lactones are valuable intermediates and precursors in organic
and polymer chemistry.1-3 Especially, β-butyrolactone is high
demand as a monomer for the production of the thermoplastic
biopolymer poly(3-hydroxybutyrate).4-6 A simple one step ring-
expansion carbonylation of epoxides to β-lactones has proved
to be industrially viable because the epoxide and carbon
monoxide starting materials are typically inexpensive.7-12
A series of well-defined [Lewis acid]+[Co(CO)4]- catalysts,
including [(salph)M]+[Co(CO)4]- and [(porphyrin)M]+[Co(CO)4]-
(M=Al3+ or Cr3+), have been developed by Coates' group for
R
R
-Co(CO)4
O
HO
I
HCo(CO)4
pathway
R
R
R
-H elimination
Scheme 1. (a) Mechanism of epoxide carbonylation (pathway A) and
ketone formation (Pathway B).
-
Co(CO)4 -incorporated Cr-MIL-101 for the continuous gas-phase
production of β-lactones from epoxides under CO at 20 bar, its
carbonylation activity (site time yield: 176 h−1) was far lower
than that of the optimized homogeneous catalyst (740 h−1).8
Therefore, the development of heterogeneous catalysts that
are efficient under mild reaction conditions is of great
importance.
Recently, we demonstrated that phthalocyanine (Pc) species
are an excellent alternative to porphyrins in epoxide
carbonylation catalysts.21 In that study, commercial aluminum
phthalocyanine chloride (AlPcCl) was reacted with Co2(CO)8 to
generate the epoxide carbonylation catalyst [AlPc]+[Co(CO)4]- in
situ. This catalyst shows efficient catalytic activity in single and
double carbonylations depending on the reaction temperature
conditions. It was envisioned that if a Pc-based heterogeneous
catalyst was used for the epoxide carbonylation, it may show an
excellent carbonylation activity, as well as an advantage on the
product separation.
epoxide carbonylation.11-18
A
mechanism for [Lewis
acid]+[Co(CO)4]--catalyzed carbonylation involving (1) epoxide
activation by the [Lewis acid]+ species; (2) ring opening by
-
Co(CO)4 ; (3) CO insertion; and (4) ring-closure was proposed
(Scheme 1, pathway A).18 Although these catalysts are highly
efficient, their industrial application may be problematic owing
to limitations in their separation and reuse.
Accordingly, our group previously reported two
heterogeneous catalysts for epoxide carbonylation to lactones
as a means of addressing these drawbacks.19,20 However, the
high pressure of CO necessary for efficient and selective
carbonylation (60 bar) hinders the study of these catalysts in
typical nonspecialized laboratories and their application in
industry. Recently, although Román-Leshkov et al. reported the
metal-organic framework-based heterogeneous catalyst
In the current study, an AlPc-based heterogenized catalyst
was rationally designed and used for epoxide carbonylation
under a CO pressure of just 10 bar and at room temperature.
The catalyst showed not only highly efficient catalytic activity
and selectivity (99%), but also functional group tolerance.
a. Department of Applied Chemistry, Kookmin University, 861-1, Jeongneung-dong,
Seongbuk-gu, Seoul 02707, Korea. E-mail: yoona@kookmin.ac.kr
Electronic Supplementary Information (ESI) is available here.
See DOI: 10.1039/x0xx00000x
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ARTICLE
Journal of Materials Chemistry A
Experimental sections
Results and Discussion
View Article Online
DOI: 10.1039/C8TA11877A
Materials and methods. Propylene oxide (PO) was distilled in a Unsubstituted metal Pcs exhibit very poor solubilities that
mixture of KOH/CaH2 under N2 atmosphere. Dimethoxyethane typically fall in the range 10−5–10−7 M in organic solvents owing
(DME) and tetrahydrofuran (THF) were distilled using to aggregation of the macrocyclic Pc units by π-π stacking.23,24
sodium/benzophenone. Allyl glycidyl ether (>99%), benzyl The introduction of bulky phenoxy substituents on peripheral Pc
glycidy ether (99%), and epichlorohydrin (>99%) were positions is one of the most effective strategies for disrupting
purchased from Sigma-Aldrich Co. without purification prior to this stacking and thus improving the solubility of metal Pcs.25,26
use. Oxetane (>98%) was supplied by TCI without further Therefore, a phenoxy-substituted AlPc was chosen for the
purification.
construction of a heterogeneous catalyst.
Synthesis of 4,5-bis(2-di-iso-propylphenoxy)phthalonitrile
ligand. The ligand was synthesized according to a previously
reported procedure with a little modification.22 Specifically, 4,5-
dichlorophthalonitrile (1.97 g, 0.01 mol), 2-isopropylphenol
(3.41 g, 0.025 mol), K2CO3 (11.04 g, 0.08 mol) were stirred in
anhydrous N,N-dimethylformamide (12 mL) at 70 °C for 36 h
under N2 atmosphere. On cooling, the reaction mixture was
poured into water (100 mL). The resulting precipitate was
filtered and washed with water, then dry in vacuum at 60 °C for
overnight. Recrystallization from methanol gave a light-blue
solid (2.51 g, 63%).
O
O
i-Pr
i-Pr
iPr
iPr
i-Pr
i-Pr
i-Pr
i-Pr
O
O
CN
CN
OH
N
N
K2CO3, DMF
AlCl3, quinoline
N
O
O
O
O
Cl
N
+
N
Al
N
70 C
nitrobenzene
210 °C, 4 h
Cl
Cl
CN
CN
iPr
N
N
i-Pr
i-Pr
i-Pr: isopropyl
O
O
1
CH2Cl2
AlCl3
Synthesis of AlPc'Cl monomer (1). 4,5-bis(2-iso-
propylphenoxy)phthalonitrile (2.38 g, 6.0 mmol) was added to
a solvent-mixture of quinoline (0.75 mL) and nitrobenzene (1.2
mL) in a 25 mL round-bottom flask. The solution was cooled in
an ice-bath and AlCl3 (0.21 g, 1.6 mmol) was added to the
mixture. The reaction was run at 210 °C for 4 h under N2. The
resulting blue-greenish solution was cooled to room
temperature and dissolved in CH2Cl2. The organic layer was
washed with HCl aqueous solution (1.0 M) and water. The crude
product was purified by column chromatography on SiO2
eluting with CH2Cl2/CH3OH (20:1) and dried at 80 °C under
vacuum for 24 h to give a dark-green solid (1.63 g, 66%).
Synthesis of the AlPc'-based porous polymer network (2). The
AlPc'Cl monomer (0.82 g, 0.5 mmol) was dissolved in CH2Cl2 (10
mL). After the solution was cooled using ice-water, the catalyst
AlCl3 (1.06 g, 8.0 mmol) was added under N2 atmosphere. The
reaction was run at 0 °C for 4 h, 26 °C for 8 h, 40 °C for 12 h,
60 °C for 12 h, and 80 °C for 24 h. The resulted precipitate was
filtered and washed with water, methanol, acetone, and THF,
respectively. Next, the resulted polymer was further purified
using Soxhlet extraction for 48 h with THF as solvent. After
drying at 120 °C in a vacuum for overnight, the product was
obtained as a deep blue powder (0.82 g, 100%).
O
O
O
O
i-Pr
i-Pr
i-Pr
i-Pr
Co(CO)4
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
O
i-Pr
N
N
N
N
N
N
Al
N
O
O
Cl
Al N
O
O
KCo(CO)4
N
N
N
O
O
O
N
THF, rt. 48 h
N
N
N
N
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
O
O
O
O
3
2
Scheme 2. Procedure for the synthesis of catalyst 3.
The synthetic process is shown in Scheme 2. First, the
monomer 1 is synthesized according to a slight modification of
a previously reported method.27,28 The solubility of the bulky
phenoxy-substituted AlPc'Cl is significantly improved compared
to that of commercial AlPcCl, enabling purification by column
chromatography. The structure of AlPc'Cl was confirmed by 1H
NMR (Fig. S1), elemental analysis (Fig. S2), and Fourier-
transform infrared (FT-IR) spectroscopy. All analytical data are
consistent with the predicted structure.
Then, the polymer network 2 are prepared from 1 and a
CH2Cl2 cross-linker via an AlCl3-catalyzed Friedel-Crafts reaction
(Scheme 2). The Friedel-Crafts reaction has been recently
demonstrated to be a valuable route to porous polymer
network that avoids the need for monomers with specific
polymerizable functionalities.29-32 This strategy has the
advantages of high yield, low cost, and easy handling. It is
worthy of note that this is the first report of the use of the
Friedel-Crafts reaction for the construction of Pc-based porous
network in the literature.33-39
Synthesis of catalyst (3). In a glove box, the network 2 (0.60 g),
KCo(CO)4 (1.61 g), and THF (15 mL) were mixed in a vial of 20
mL. The suspension was filtered and washed several times with
THF after stirring for 48 h at room temperature. The obtained
catalyst was purified two times using the process of dispersion
several hours/filtration/washing. The product was given after
drying under vacuum (0.59 g, 98%).
Epoxide carbonylation. In a typical procedure, the catalyst (20
mg, 1.75 wt% of cobalt determined from an inductively coupled
plasma atomic emission spectroscopy (ICP-AES)) was added into
a 100-mL stainless steel reactor in a glove box. After the reactor
was flushed with CO, the prepared PO solution in DME (0.1 M,
1.54 g) was injected into the reactor under CO flow. The
reaction was run at room temperature for 1 h under 10-bar CO.
The reaction solution was transferred to a vial after cooling the
reactor and releasing excess CO. The crude product was
analyzed by 1H NMR spectrum with naphthalene as an internal
standard.
The prepared 2 is insoluble in nearly all organic solvents. The
scanning electron microscopy (SEM) image of 2 (Fig. 1a) reveals
that it has a morphology comprising aggregated spherical
nanoparticles. The transmission electron microscope (TEM)
image of 2 clearly showed the presence of hierarchical nano-
sized pores on the network surface (Fig. 1b and Fig. S3). IR
measurement was performed to confirm the formation and
chemical structure of 2 (Fig. 1c). For the monomer 1, the IR
absorption peak at 3070 cm−1 is characteristic of the C-H bonds
on the aromatic ring and the peaks at 1450 cm−1 and 1340 cm−1
correspond to the C=N and C-N stretching vibrations,
2 | J. Name., 2012, 00, 1-3
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of 2 revealed an amorphous peak at 2θ = 21°, indicating that the
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bulky phenoxy substituents prevent the clDoOseI: p10a.c10k3in9/gCo8fTAth11e87P7cA'
units (Fig. S6). Therefore, the introduction of bulky phenoxy
substituents to the peripheral Pc positions is crucial for the
prevention of Pc unit aggregation and thus for knitting the
monomers together to form a network.
The Al content of 2 was evaluated using energy-dispersive X-
ray (EDX) spectroscopy and ICP-AES. EDX analysis revealed that
84.2% of the Pc' rings was coordinated to Al atoms in 2 (Al: 1.29
wt%) based on the calculation of the Al/N atomic ratio (Fig. S7).
ICP-AES revealed that the Al content in 2 is 1.26 wt%, which is
close to the value from the EDX analysis. This high metal content
is attributed to the fact that the network 2 is prepared by direct
polymerization of metalated Pc' monomers rather than post-
metalation of a porous organic polymer.19,20,44
-
To replace Cl- in 2 with Co(CO)4 , the network 2 were treated
with excess KCo(CO)4 to provide
a green catalyst in
stoichiometric yield. The SEM image of the catalyst 3
demonstrates that the morphology of the network is not
changed during the KCo(CO)4 reaction (Fig. S8). An IR peak at
1883 cm−1, which is attributed to absorption by the CO in
-
Co(CO)4 , is presented by the product (Fig. 1c). The Co anion in
the catalyst 3 was investigated using X-ray photoelectron
spectroscopy (XPS), revealing a Co- (2p1/2) peak at 797.8 eV and
a Co- (2p3/2) peak at 782.3 eV, similar to those observed in our
previous studies (Fig. 1e).19,20 XPS also revealed that the Al (2p)
electron binding energy (74.3 eV) is 0.5 eV lower than that of
the network 2 (Fig. S9), further demonstrating the success of the
anion exchange reaction. ICP-AES revealed that the Al/Co
atomic ratio of the catalyst 3 is 1:0.65, which is close to that
revealed by the EDX data (Al/Co = 1:0.61, Fig. S10). These results
indicate that approximately 65% of the Al sites are paired with
Fig. 1 Characterization of the network 2 and catalyst 3 using SEM (a),
TEM (b), FT-IR (c), solid-state 13C NMR (d), XPS (e) and BET (f).
-
Co(CO)4 . The other 35% of the Al sites may exist as ion pairs
respectively.40-42 After the Friedel-Crafts reaction, the
characteristic C=N and C-N bond vibrations remain, indicating
that the Pc' ring is sufficiently stable during the reaction, and
the intensity of the peak at 3070 cm−1 is reduced significantly,
suggesting that the aromatic ring is alkylated and confirming the
formation of methylene linkages. This result is consistent with
those of previous studies in which the intensity of the aromatic
group signal is decreased upon Friedel-Crafts reaction.43
Elemental analysis is a very useful tool for the composition
characterization of the network 2. Elemental analysis of the
network 2 indicated that the actual C/N molar ratio (14.9) is
higher than the predicated value (14.0), as illustrated in Scheme
1b, further indicating multiple alkylation of the aromatic ring
(Fig. S4). Compared to monomer 1, the solid-state 13C NMR
spectrum of the network 2 showed additional signals at 43 ppm
and 49 ppm, which may be attributed to the carbon atoms in
the methylene linker (Fig. 1d and Fig. S5). This result is in
agreement with those previously reported for crosslinked
aromatic rings using similar methods.29,31 The signals at δ = 153,
132, and 111 ppm corresponded to the carbon atoms of the
phthalocyanine and aromatic groups. Based on the above
analyses, the alkylation of the aromatic ring is confirmed and
the chemical structure of the Pc' ring remains intact without
decomposition during the Friedel-Crafts reaction.
with Cl- as a counter ion. The reason for the partial replacement
may be the high degree of cross-linking in the network, resulting
in not all the Cl- sites being available for ion-exchange.
To evaluate the porosities of the network 2 and catalyst 3,
Brunauer-Emmet-Teller (BET) analysis at 77 K was performed.
The shapes of the sorption isotherms (Fig. 1f) indicate wide
pore-size distributions. The rapid uptake of nitrogen gas in the
low-relative-pressure regions (P/P0 <0.001) is due to the filling
of micropores, while the obvious hysteresis and sharp rise in the
high-relative-pressure regions (P/P0 >0.9) indicates the
presence of mesopores and macropores in the network
according to the Barrett-Joyner-Halenda model (Fig. S11). The
BET surface areas of 2 and 3 are 660 and 470 m2 g−1 with pore
volumes of 0.6 and 0.4 cm3 g−1, respectively. These results
indicate that the network-bound Cl- (approximately 65%) is
-
substituted by Co(CO)4 , resulting in the inclusion of Co(CO)4- in
the network.
Considering that the catalyst generated in situ by the
commercially available AlPcCl and Co2(CO)8 has been shown to
have efficient carbonylation activity at room temperature,21 the
carbonylation reactions used to evaluate the catalytic activity of
catalyst 3 in the present study were conducted at room
temperature. First, PO carbonylation was performed in DME
using the heterogeneous catalyst at room temperature (23 °C)
for 1 h under a CO pressure of 40 bar in a 100-mL stainless steel
tube reactor. Full conversion of PO was confirmed using 1H NMR
spectroscopy, resulting in a 95% yield of β-butyrolactone and a
molar ratio of β-butyrolactone to acetone of >99:1, which is
In comparison, if commercial AlPcCl is employed under the
same reaction conditions, no insoluble product (e.g., in CH3OH)
is afforded. This result indicates that the commercial AlPcCl
monomer exhibits a lower Friedel-Crafts reactivity than that of
1 and therefore the knitting together of aromatic rings in the
monomer does not proceed. Powder X-ray diffraction analysis
This journal is © The Royal Society of Chemistry 20xx
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ARTICLE
Journal of Materials Chemistry A
similar to our reported result for the in situ homogeneous
catalyst (Table 1, entry 1, Fig. S12).
The solvent dependence of the carbonylation activity in the
heterogeneous catalyst is consistent with thaVtiewofArtiCcloe Oatnelinse'
DOI: 10.1039/C8TA11877A
Significantly, if low-pressure CO (10 bar) is used for the homogeneous systems.18 Weakly coordinating solvents (e.g.,
carbonylation under otherwise identical reaction condition, DME) show higher activity than more strongly coordinating
very similar results to that using a CO pressure of 40 bar are solvents (e.g., THF) (Fig. S18).
achieved (Table 1, entry 2, Fig. S13). In other words, the product
To demonstrate the catalytic synergy between the network Al
-
selectivity is not affected by using different CO pressures in the sites and Co(CO)4 , the network 2 and KCo(CO)4 were used
range 10–40 bar. In contrast, our previously reported separately for oxetane carbonylation. As expected, no γ-
heterogeneous catalysts and different Coates' homogeneous butyrolactone formation was observed, probably due to the
-
catalysts show much higher selectivities for the ketone side lack of Co(CO)4 for CO insertion and an appropriate [Lewis
products under relatively low CO pressures (<15 bar).16,17,19,45 acid]+ species for oxetane activation (Fig. S19). Notably, an
One possible explanation for this difference is that the AlPc'- equimolar mixture of the network 2 and KCo(CO)4 promotes γ-
based catalyst promotes faster ring-closing than ketone butyrolactone formation to some extent. This may be attributed
generation. The generation of ketone products occurs via β- to partial in situ formation of Al/Co sites resulting in fractional
elimination by the intermediate
protonation and rearrangement in two stages and consistent much lower than that achieved using the network 2 containing
I followed by enolate carbonylation activity for the mixture. However, the yield is
-
with Coates' work (Scheme 1, pathway B).18
post-synthetically introduced Co(CO)4 (Fig. S20). Notably,
Subsequently, the activity and selectivity of the Román-Leshkov’s group reported a similar carbonylation
heterogeneous catalyst was evaluated using other substrates
under 10-bar CO at room temperature. In the case of glycidyl
ethers with functional groups (e.g., allyl or benzyl), full
conversion of the starting material is achieved and the
selectivity for lactones is >99% (Table 1, entries 3 and 4, Figs.
S14 and S15). Epichlorohydrin, a traditionally challenging
substrate for carbonylation, shows similar selectivity and
activity to those of the glycidyl ethers (Table 1, entry 5, Fig. S16).
Only one catalyst reported in the literature effects quantitative
carbonylation of epichlorohydrin.8,10,13,14,17 Oxetane has a lower
ring-strain energy than three-membered epoxides and
consequently few catalysts have been reported for its
carbonylation.11,46-49 However, our AlPc'-based heterogeneous
catalyst exhibits oxetane-carbonylation activity, even at room
temperature and under 10-bar CO (Table 1, entry 6, Fig. S17).
These results reveal that the AlPc'-based heterogeneous
catalyst not only exhibits functional group tolerance but also
efficient activity and high selectivity in the carbonylation of
oxygen-containing rings.
activity using an in situ generated catalyst derived from Cr-MIL-
101 and Na[Co(CO)4].8 It is believed that the co-existence of
-
both a Lewis acid with appropriate acidity and Co(CO)4 is
necessary for efficient carbonylation.
The heterogeneous nature of the catalyst 3 was confirmed
using a filtration test. Specifically, the catalyst 3 in a PO
carbonylation mixture was filtered after reaction for 1 h, and
the PO carbonylation in the resulting colorless filtrate was
assessed. Even when the reaction time was extended to 24 h,
the β-butyrolactone concentration did not increase and
unreacted PO was detected in the mixture (Fig. S21), confirming
that the catalyst is heterogeneous in nature.
Table 2. Recyclability of catalyst for PO carbonylation.a
Cycle Yield (%) β-butyrolactone:Acetoneb
1
2
3
4d
94
92
75c
95
> 99:1
> 99:1
> 99:1
> 99:1
Table 1. Carbonylation of different substrates using the catalyst
3.a
aReaction conditions: catalyst 50 mg; DME; feed molar
b
1
PO/cobalt ratio 30; CO 10 bar; 23 °C, 1 h. Determined by H
NMR spectroscopy. cUnreacted PO. dRegenerated catalyst used
for PO carbonylation.
Tim
e
(h)
CO
(bar)
Yield Lactone:
No
substrate
(%)b
ketoneb
O
O
1
2
40
10
1
1
95
94
>99 <1
>99 <1
>99 <1
To evaluate the recyclability of the heterogeneous catalyst,
the green solid was recovered after the initial run using simple
filtration, washed with DME, and used directly for the next run.
The catalytic performance of the recovered catalyst is shown in
Table 2. In the second cycle, the ratio of β-butyrolactone to
acetone is maintained at >99:1. However, the yield of β-
butyrolactone in the third run is decreased from 94% to 75%, a
19% reduction. After three catalytic cycles, the SEM images
showed no morphological change of the catalyst 3 (Fig. S22).
The BET surface area and pore volume of the catalyst 3 after
three cycles is 390 m2 g-1 and 0.3 cm3 g-1, respectively, which is
slightly lower than that of fresh catalyst 3 (470 m2 g-1, 0.4 cm3 g-
1), demonstrating the porous structure is still existed (Fig S23).
ICP showed that there were no Al species in the filtrate after
each cycle, but that some Co was present, indicating that the
reduction in activity of the catalyst 3 can be attributed to the
O
3
4
10
10
22
22
98
97
O
O
>99 <1
>99 <1
O
O
5
6
10
10
22
22
97
96
Cl
O
>99
--
aThe feed molar substrate/Co ratio was 30. bYields and
lactone/ketone ratios determined by 1H NMR with naphthalene
as an internal standard. A substrate solution prepared with DME
(0.1 M, 1.54 g) was injected into the reactor with the catalyst
(20 mg) under CO flow.
-
leaching of Co(CO)4 . Notably, the catalytic performance of the
4 | J. Name., 2012, 00, 1-3
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catalyst after successive runs is restored by treating it with 22 S. Mori, M. Nagata, Y. Nakahata, K. Yasuta, R. GoVtioew, MArt.icKleimOnulirnae
KCo(CO)4 (Table 2, entry 4).
and M. Taya, J. Am. Chem. Soc., 2010, 132, 4054.
23 F. Ghani, J. Kristen and H. Riegler, J. Chem. Eng. Data, 2012, 57,
439.
DOI: 10.1039/C8TA11877A
24 C. G. Chao and D. E. Bergbreiter, Catal. Commun., 2016, 77, 89.
25 N. B. McKeown, S. Makhseed, K. J. Msayib, L. L. Ooi, M. Helliwell
and J. E. Warren, Angew. Chem. Int. Ed., 2005, 44, 7546.
26 S. Makhseed, J. Samuel and F. Ibrahim, Tetrahedron, 2008, 64,
8871.
27 F. Santerre, R. Côté, G. Veilleux, R. G. Saint-Jacques and J. P.
Dodelet, J. Phys. Chem. 1996, 100, 7632.
28 H. Raboui, M. Al-Amar, A. I. Abdelrahman and T. P. Bender, RSC
Adv., 2015, 5, 45731.
29 B. Li, R. Gong, W. Wang, X. Huang, W. Zhang, H. Li, C. Hu and B.
Tan, Macromolecules, 2011, 44, 2410.
Conclusions
A
novel
heterogeneous
catalyst,
[AlPc'-based
porous
network]+[Co(CO)4]-, was rationally designed and prepared for
epoxide carbonylation. The synthesis of the catalyst involves a facile
Friedel-Crafts alkylation of AlPc'Cl monomers and subsequent
-
replacement of Cl- with Co(CO)4 . The heterogeneous catalyst
showed efficient activity and high selectivity for epoxide
carbonylation under a lower CO pressure and reaction temperature
than those previously reported for similar catalysts, as well as
excellent functional group tolerance. Considering the favorable
catalytic performance of AlPc'-based heterogeneous catalyst under
mild reaction condition, the application of this catalyst for epoxide
carbonylation in gas-phase reactors is currently in progress.
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