CO2 transformation under mild conditions using tripolyphosphate-grafted KCC-1-NH2

Article abstract of DOI:10.1080/10426507.2018.1455197

Fibrous nanosilica (KCC-1) as a catalyst support was investigated in terms of stability, recycling, and reusability. For the first time, CO₂ transformation was performed via the synthesis and application of KCC-1 together with sodium tripolyphosphate (STPP) and 3-aminopropyltriethoxysilane (APTES) as its functionalized derivative. To this goal, KCC-1/STPP NPs were applied to act as a nanocatalyst with excellent catalytic activities under green reaction conditions.

Full text of DOI:10.1080/10426507.2018.1455197

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
CO2 transformation under mild conditions using
tripolyphosphate-grafted KCC-1-NH2
Seyed Mohsen Sadeghzadeh, Rahele Zhiani & Marjan Moradi
To cite this article: Seyed Mohsen Sadeghzadeh, Rahele Zhiani & Marjan Moradi (2018): CO2
transformation under mild conditions using tripolyphosphate-grafted KCC-1-NH2, Phosphorus,
Sulfur, and Silicon and the Related Elements, DOI: 10.1080/10426507.2018.1455197
To link to this article: https://doi.org/10.1080/10426507.2018.1455197
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Publisher: Taylor & Francis
Journal: Phosphorus, Sulfur, and Silicon and the Related Elements
DOI: https://doi.org/10.1080/10426507.2018.1455197
CO2 transformation under mild conditions using tripolyphosphate-grafted
KCC-1-NH2
Seyed Mohsen Sadeghzadeh, Rahele Zhiani, Marjan Moradi
Department of Chemistry, Faculty of Sciences, Neyshabur Branch, Islamic Azad University,
Neyshabur, Iran.
E-mail: seyedmohsen.sadeghzadeh@gmail.com
Abstract
Fibrous nanosilica (KCC-1) as a catalyst support was investigated in terms of stability, recycling, and
reusability. For the first time, CO2 transformation was performed via the synthesis and application of
KCC-1 together with sodium tripolyphosphate (STPP) and 3-aminopropyltriethoxysilane (APTES) as
its functionalized derivative. To this goal, KCC-1/STPP NPs were applied to act as a nanocatalyst
with excellent catalytic activities under green reaction conditions.
Keywords
Carbon dioxide, Nanoparticles (NPs), Green chemistry, TPP, KCC-1
Introduction
Green chemistry has recently attracted attention for coping with the difficulty of the
transformation of CO2 as a greenhouse gas. This problem can be solved by the application of
CO2 as a cheap, renewable, and safe C1 building block for synthesizing dimethyl carbonate
(DMC) [1-2], formic acid (FA) [3], carbamic esters (urethanes) [4], cyclic carbonates (CCs)
Corresponding author. Tel./fax:+98 561 2502065; e-mail: seyedmohsen.sadeghzadeh@gmail.com

[5], methanol [6], and polycarbonates (PCs) [7] as useful organic compounds. CO2 can be
also used for carboxylative cyclization of propargylic amines to synthesize 2-oxazolidinones
that significantly act as chemical intermediates [8] and chiral auxiliaries [9] and play an
important role in antibacterial drugs [10]. CO2 may be fixed by the mentioned process, which
provides a very clean atom-economic reaction.
Periodic MesoporousOrganosilicas (PMOs) have been identified as a new class of
functionalized ordered nanoporoussilicas. They aresynthesized by simultaneously
hydrolyzing and condensing organic-bridged alkoxysilane precursors. These materials have
been recently studied for their high surface areas, tuneable pore sizes and volumes, robust
stabilities, and excellent lipophilicities. Compared to ordered mesoporoussilicas carrying
terminal functional groups, PMOs have their functional groups embedded homogeneously
inside their walls instead of pore fibers, thus providing an improved mechanical and
hydrothermal stability. Numerous PMOs have recently been employed in association with
their varied bridging ligands of organic functional groups as supporters and catalysts in
several chemical processes. In a typical chemical process, their metal contents can be readily
recovered and reused [11-22]. Preparation of metal-containing PMOs is usually performed by
either impregnating metal complexes into PMO samples with proper ligands or hydrolyzing
and co-condensing tetraethyl orthosilicate (TEOS) bridged with metal complexes in the
presence of cationic surfactant as a template.
KCC-1 serves as an excellent nominated support for designing efficient nanocatalysts that
satisfy the desired conditions. KCC-1 high surface area is its unique feature resulted from its
fibrous morphology rather than mesoporous channels found in SBA-15 and MCM-41 [23-
28]. Functionalization has been previously reported to be done through modification of KCC-
1 fibers following its synthesis. During the modification process, KCC-1-NH2 is involved in a
reaction with APTES and then as a ligand or pseudo-chelator for controlling metal leaching
[29-34]. In this study, the effectiveness of KCC-1 fibrous morphology in a variety of
applications was compared with that of the conventional ordered mesoporous silica. Mild
reaction conditions were considered for this green catalyst [35-39]. We developed a new
stable and sustainable catalyst support via KCC-1/STPP bond [40]. We believe that this
unique silica-supported catalyst is very useful as providing significantly enhanced
accessibility to active sites. As a nano-labyrinth, KCC-1/STPP holds STPP, which is used for
chemoselectively synthesizing CCs (Scheme 1).
Results anddiscussion
2

The structure of the KCC-1/ATPP proposed interaction of tripolyphosphate with
aminopropyltriethoxysilane within the fibers of KCC-1 is shown in scheme 2. We were intrigued by
the possibility of applying nanotechnology for designing a novel, active, and recyclable recoverable
nano-catalyst.
Having proven the correct and complete synthesis of the catalyst, its performance and stability were
tested by the syntheses of compounds 1-4. To optimize the reaction conditions and obtain the best
catalytic activity, the reaction of CO2 and 1-butyl-2-phenylaziridine for the synthesis of 5-aryl-2-
oxazolidinones (Compound 1), the reaction of CO2 and 2-methy-4-phenylbut-3-yn-2-ol for the
synthesis of α-alkylidene CCs (Compound 2), the reaction of CO2 and propylene oxide for the
preparation of CCs (Compound 3), and the reaction of CO2 and 2-aminobenzonitrile for the synthesis
of quinazoline-2,4(1H,3H)-dione (Compound 4) were employed as the desired models to be
conducted under different reaction parameters, such as catalyst amount, temperature, time, and
solvent. Initially, the reactions were carried out in several solvents to study the catalyst efficiency. In
this research, conventional heating was applied for the synthesis of Compound 1 in the presence 0.7
mg of the catalyst at a CO2 pressure of 0.5 bar at room temperature for 30 min under solvent-free
conditions. The conditions for the synthesis of Compound 2 in the presence 0.7 mg of the catalyst
included heating at 80oC at a CO2 pressure of 1 bar for 120 min under solvent-free conditions. The
synthesis of Compound 3 in the presence of 0.7 mg of the catalyst was conducted by heating it at
100oC at a CO2 pressure of 1 bar for 60 min under solvent-free conditions. Finally, the more efficient
conditions of heating at 70oC in the presence of 0.7 mg of the catalyst at a CO2 pressure of 1.5 bar for
50 min under solvent-free conditions were found for the synthesis of Compound 4 (Table 1).
For further investigating the catalyst efficiency, different control experiments were performed, the
information of which are displayed in Table 2. Initially, the standard reaction with KCC-1 revealed
the formation of none of the desired product after 1 h of the reaction time (Table 2, Entry 1). Also, no
reaction was observed when KCC-1–NH2 was utilized as the catalyst (Table 2, Entry 2). APTES
could not provide a satisfactory catalytic activity under mild reactions. Based on these disappointing
results, we continued the studies to ameliorate the product yield by adding tripolyphosphate (TPP).
Notably, there were many differences in the reaction yields when the reaction was carried out with
KCC-1/STPP NPs and TPP nano-catalyst. These results demonstrated that –NH2 and TPP did not
have any catalytic roles individually (Table 2, Entries 2 and 3). These observations showed that the
reaction cycle was simultaneously catalyzed by –NH2 and TPP species supports on KCC-1/STPP
nanostructure (Table 2, Entry 4). Thus, KCC-1/STPP was applied in the subsequent studies because of
its high reactivity and selectivity and easy separation. Also, the nano-catalyst activity and selectivity
could be manipulated by tailoring its chemical and physical properties, such as size, shape,
composition, and morphology. To assess the exact impact of KCC-1 presence in the catalyst, KCC-
3

1/STPP NPs were compared with SiO2/ATPP NPs. To this end, we examined SiO2/STPP and KCC-
1/ATPP NPs, which had similar compositions, but different structures. When SiO2/STPP was used as
the catalyst, the desired product showed a fair-to-average yield, while KCC-1/STPP NPs provided a
good yield (Table 2, Entries 4 and 5).
study the prospective and general applicability of the developed protocol, the carboxylative
cyclization reactions of CO2 with a variety of aziridines were examined under optimized reaction
conditions (Table 3). TPP-functionalized KCC-1-NH2 NPs had a very high basic catalytic activity
and excellent regioselectivity towards the cycloaddition of CO2 with aziridines. In each case, 5-aryl-
2-oxazolidinones were obtained with excellent isolated yields in the presence of KCC-1/STPP
(Scheme 3).
Propargyl alcohols associated with a variety of alkyl and aryl substituents at the propargylic position
were effective substrates to give the corresponding carbonates of 2a–2d with good-to-excellent yields
even under the mentioned CO2 conditions (Scheme 4, Table 4).
Since KCC-1/STPP was the most active one-component catalyst, it was tested for the conversions of
other terminal epoxides into the corresponding CCs (3a–l) (Scheme 5), the results of which are
exhibited in Table 5. In each case, CCs were obtained with good-to-excellent isolated yields after 100
min using 0.7 mg of the catalyst at a constant CO2 pressure at 100oC under solvent-free conditions.
KCC-1/STPP was also tested for the conversions of the other six 2-aminobenzonitriles into
quinazoline-2,4(1H,3H)-diones (4a–f) (Scheme 6), the results of which are represented in Table 6. In
each case, quinazoline-2,4(1H,3H)-diones were obtained with good-to-excellent isolated yields in the
presence of KCC-1/STPP NPs.
We compared the catalytic performance of our catalyst with those reported for the syntheses of 5-aryl-
2-oxazolidinone, α-alkylidene CC, quinazoline-2,4(1H,3H)-dione, and CCs in the literature. Tables 7-
10 clearly demonstrate that a lower temperature and CO2 pressure, minimum catalyst amount, and
shorter reaction time are required for CO2 transformation using KCC-1/STPP NPs. (see also Figure S
1, Supplemental Materials).
It is important to note that the heterogeneous property of KCC-1/STPP facilitates its efficient recovery
from the reaction mixture during the work-up procedure. The activity of the recycled catalyst was also
examined under the optimized conditions. After the completion of the reaction, the catalyst was
separated by filtration, washed with methanol, and dried at the pump. The recovered catalyst was
reused for 10 consecutive cycles without any significant loss of the catalytic activity (Figure S1).
Inductively Coupled Plasma (ICP) analysis showed that the amount of STPP leaching into the
4

reaction mixture was very low (0.3 ppm). These observations indicated that the catalyst was stable
and could tolerate the present reaction conditions.
Experimental
Materials and Methods
The chemical materials were purchased from Fluka and Merck in high purities. Their melting points
determined in open capillaries by using an Electrothermal 9100 apparatus were uncorrected. FT-IR
spectra were recorded on a VERTEX 70 spectrometer (Bruker) in the transmission mode in
spectroscopic grade KBr pellets for all the powders. Their morphologies were analyzed using High-
Resolution Transmission Electron Microscopy (HRTEM) on a JEOL transmission electron
microscope operating at 200 kV. The phosphorous content of the catalyst was determined by an
OPTIMA 7300DV ICP analyzer. The X-ray powder diffraction data were obtained by using Bruker
D8 Advance with Cu karadition. The Thermo-Gravimetric Analysis (TGA) was carried out on a
NETZSCH STA449F3 at a heating rate of 10°C min−1 under nitrogen. NMR spectra were recorded in
CDCl3 on a BrukerAvance DRX-400 MHz spectrometer using tetramethylsilane (TMS) as an internal
standard. The purity determinations of the products and reaction monitoring were accomplished by
TLC on silica-gel polygram SILG/UV 254 plates.
General Procedure for the Preparation of KCC-1 NPs
Tetraethylorthosilicate (TEOS) (2.5 g) was dissolved in a solution of cyclohexane (30 mL) and 1-
pentanol (1.5 mL). A stirred solution of cetylpyridinium bromide (CPB 1 g) and urea (0.6 g) in water
(30 mL) was then added. The resulting mixture was continually stirred at room temperature for 45
min and then placed in a teflon-sealed hydrothermal reactor to be heated at 120°C for 5 h. The formed
silica was isolated by centrifugation, washed with deionized water and acetone, and dried in a drying
oven. This material was then calcined in air at 550°C for 5 h. [41]
General Procedure for the Preparation of KCC-1-NH2 NPs
KCC-1 NPs (2 mmol) and THF (20 mL) were mixed together in a beaker and then, NaH (20 mmol)
was dispersed in the mixture via ultrasonication. APTES (22 mmol) was added drop-wise at room
temperature and stirred at 60°C for further 16 h. The resultant products were collected and washed
with ethanol and deionized water in sequence and then dried under vacuum at 60°C for 2 h for further
use [41].
General Procedure for the Preparation of KCC-1/ATPP NPs
TPP (5 mmol) was dispersed in dry CH2Cl2 (20 mL), to which KCC-1-NH2 (0.1 g) nanoparticles were
then added. Afterwards, the mixture was heated up to 60°C under nitrogen atmosphere for 12 h. The
5

resulting solid was separated by filtration and washed 3 times with CH2Cl2, ethanol, and water. After
drying it under vacuum at room temperature, KCC-1/STPP was obtained as a white powder [41].
General procedures for preparation of 5-aryl-2-oxazolidinones (Compound 1)
1-butyl-2-phenylaziridine (1 mmol) and KCC-1/STPP NPs (0.7 mg) were mixed together. The
autoclave was closed, purged twice with CO2 gas, pressurized to 0.5 MPa of CO2, and heated at room
temperature for 30 min. Then, the reactor was cooled to ambient temperature and the resulting
mixture was transferred to a 50 mL round-bottom flask. During completion, the reaction progress was
monitored by TLC. After completion, EtOH was added to the reaction mixture and the catalyst was
separated by filtration. Then, the solvent was removed from the solution under reduced pressure and
the resulting product was purified by recrystallization using n-hexane/ethyl acetate.
General procedures for preparation of α-alkylidene cyclic carbonates(Compound 2)
KCC-1/STPP NPs (0.7 mg) and 2-methy-4-phenylbut-3-yn-2-ol (1 mmol) were charged into the
reactor vessel without using any co-solvent. The reactor vessel was placed under 1 MPa of CO2 and
then heated to 80oC for 120 min. Next, the reactor was cooled to ambient temperature and the
resulting mixture was transferred to a 50-mL round-bottom flask. During completion, the reaction
progress was monitored by TLC. Upon completion, EtOH was added to the reaction mixture and the
catalyst was separated by filtration. Then, the solvent was removed from the solution under reduced
pressure and the resulting product was purified by recrystallization using n-hexane/ethyl acetate.
General procedures for preparation of cyclic carbonate (Compound 3)
KCC-1/STPP NPs (0.7 mg) and epoxide (1 mmol) were charged into the reactor vessel without using
any co-solvent. The reactor vessel was placed under 1 MPa of CO2 and heated to 100oC for 60 min.
Then, the reactor was cooled to ambient temperature and the resulting mixture was transferred to a 50
mL round-bottom flask. During completion, the reaction progress was monitored by TLC. After being
completed, EtOH was added to the reaction mixture and the catalyst was separated by filtration. Next,
the solvent was removed from the solution under reduced pressure and the resulting product was
purified by recrystallization using n-hexane/ethyl acetate.
General procedures for preparation of quinazoline-2,4(1H,3H)-dione (Compound 4)
2-aminobenzonitrile (1 mmol) and KCC-1/STPP NPs (0.7 mg) were mixed together. The autoclave
was closed, purged twice with CO2 gas, pressurized to 1.5 MPa of CO2, and heated at 70oC for 50
min. Then, the reactor was cooled to ambient temperature and the resulting mixture was transferred to
a 50 mL round-bottom flask. During completion, the reaction progress was monitored by TLC.
Following its completion, EtOH was added to the reaction mixture and the catalyst was separated by
6

filtration. Afterwards, the solvent was removed from the solution under reduced pressure and the
resulting product was purified by recrystallization using n-hexane/ethyl acetate. The products are
known and their sample characterization data is presented in the Supplemental Materials.
Conclusions
In summary, we reported a novel design of a catalyst support via KCC-1-NH2 bond of TPP
(KCC-1/STPP), which exhibited an excellent catalytic activity with the syntheses of 5-aryl-2-
oxazolidinones, α-alkylidene CCs, CC, and quinazoline-2,4(1H,3H)-dione. This synthetic
method provided a green method for effectively preparing a low-cost ionic liquid-based
catalyst as a promising approach to the development of other useful materials. The significant
features of this newly developed procedure were easy separation of the catalyst from the
reaction mixture based on heterogeneous properties, as well as its reusability, operational
simplicity, and high yields.
References
1 He, J. M.; Sun, Y.; Han, B. Angew. Chem., Int. Ed., 2013, 52, 9620-9633.
2 Honda, M.; Tamura, M.; Nakagawa, Y.; Tomishige, K. Catal. Sci. Technol., 2014, 4,
2830-2845.
3 Tanaka, R.; Yamashita, M.; Nozaki, K. J. Am. Chem. Soc., 2009, 131, 14168-14169.
4 Yoshida, M.; Hara, N.; Okuyama, S. Chem. Commun., 2000, 36, 151-152.
5 Vara, B. A.; Struble, T. J.; Wang, W.; Dobish, M. C.; Johnston, J. N. J. Am. Chem.
Soc.,2015, 137, 7302-7305.
6 Wesselbaum, S.; vomStein, T.; Klankermayer, J.; Leitner, W. Angew. Chem., Int. Ed.,
2012, 51, 7499-7502.
7 Darensbourg, D. J.; Moncada, A. I.; Choi, W.; Reibenspies, J. H. J. Am. Chem. Soc.,
2008, 130, 6523-6533.
8 Aurelio, L.; Brownlee, R. T. C.; Hughes, A. B. Chem. Rev.,2004, 104, 5823-5846.
9 Chung, C. W. Y.; Toy, P. H. Tetrahedron: Asymmetry, 2004, 15, 387-399.
10 Mukhtar, T. A.; Wright, G. D. Chem. Rev.,2005, 105, 529-542.
11 Wan, H.; Wu, Z.; Chen, W.; Guan, G.;Cai, Y.; Chen, C.; Li, Z.; Liu, X. J. Mol. Catal.
A: Chem., 2015, 398, 127-132.
12 Litschauer, M.;Neouze, M.A. J. Mater. Chem., 2008, 18, 640-646.
7

13 Sadeghzadeh, S.M. Catal. Sci. Technol., 2016, 6, 1435–1441.
14 Zhang, Y.; Zhang, Y.; Pei, Q.;Feng, T.; Mao, H.; Zhang, W.; Wu, S.; Liu, D.; Wang,
H.; Song, X.M. Appl. Surf. Sci., 2015, 346, 194-200.
15 Li, P.H.; Li, B.L.; Hu, H.C.; Zhao, X.N.; Zhang, Z.H. Catal. Commun. 2014, 46, 118-
122.
16 Sobhani, S.;Honarmand, M. Appl. Catal., A, 2013, 467, 456-462.
17 Hamadi, H.;Kooti, M.;Afshari, M.;Ghiasifar, Z.; Adibpour, N. J. Mol. Catal. A:
Chem.2013, 373, 25-29.
18 Liu, Y.;Tian, A.; Wang, X.; Qi, J.; Wang, F.; Ma, Y.; Ito, Y.; Wei, Y. J. Chromatogr.
A, 2015, 1400, 40-46.
19 Liu, W.; Wang, D.;Duan, Y.; Zhang, Y.;Bian, F. Tetrahedron Lett., 2015, 56, 1784-
1789.
20 Sadeghzadeh, S.M. Catal. Commun., 2015, 72, 91-96.
21 Sadeghzadeh, S. M. Microporous Mesoporous Mater., 2016, 234, 310-316.
22 Wang, P.; Kong, A.G.; Wang, W.J.; Zhu, H.Y.; Shan, Y.K. Catal. Lett., 2010, 135,
159-164.
23 Sadeghzadeh, S. M. RSC Adv., 2015, 5, 68947-68952.
24 Sadeghzadeh, S.M.; Zhiani, R.; Emrani, S.; Abasian, M. J. Organomet. Chem., 2018,
855, 1-6.
25 Polshettiwar, V.; Cha, D.; Zhang, X. X.; Basset, J. M. Angew. Chem., Int. Ed., 2010,
49, 9652-9656.
26 Lilly Thankamony, A.S.; Lion, C.; Pourpoint, F.; Singh, B.; Perez Linde, A.J.;
Carnevale, D.; Bodenhausen, G.; Vezin, H.; Lafon, O.; Polshettiwar, V. Angew.
Chem., Int. Ed. 2015, 54, 2190-2193.
27 Bouhrara, M.; Ranga, C.; Fihri, A.; Shaikh, R. R.; Sarawade, P.; Emwas, A. H.;
Hedhili, M. N.; Polshettiwar, V. ACS Sustainable Chem. Eng., 2013, 1, 1192-1199.
28 Dhiman, M.; Chalke, B.; Polshettiwar, V. ACS Sustainable Chem. Eng., 2015, 3,
3224-3230.
29 Fihri, A.; Bouhrara, M.; Cha, D.; Almana, N.; Polshettiwar, V. ChemSusChem 2012,
5, 85-89.
30 Fihri, A.; Bouhrara, M.; Patil, U.; Cha, D.; Saih, Y.; Polshettiwar, V. ACS Catal.,
2012, 2, 1425-1431.
31 Sadeghzadeh, S.M.; Zhiani, R.; Emrani, S.RSC Adv., 2017, 7,24885-24894.
8

32 Le, X.; Dong, Z.; Liu, Y.; Jin, Z. Huy, T. D.;Leb, M,; Ma, J. J. Mater. Chem. A, 2014,
2, 19696-19706.
33 Le, X.; Dong, Z.; Li, X.; Zhang, W.; Le, M.; Ma, J.Catal. Commun., 2015, 59, 21-25.
34 Sadeghzadeh, S.M.; Zhiani, R.; Emrani, S. RSC Adv., 2017, 7, 32139-32145.
35 Singh, R.; Bapat, R.; Qin, L.; Feng, H.; Polshettiwar, V. ACS Catal., 2016, 6, 2770-
2784.
36 Sun, Z.; Li, H.; Guo, D.; Sun, J.; Cui, G.; Liu, Y.; Tian, Y.; Yan, S. J. Mater. Chem.
C, 2015, 3, 4713-4722.
37 Yu, K.; Zhang, X.; Tong, H.; Yan, X.; Liu, S. Mater. Lett. 2013, 106, 151-154.
38 Dong, Z.; Le, X.; Dong, C.; Zhang, W.; Li, X.; Ma, J. Appl. Catal., B, 2015, 162, 372-
380.
39 Dong, Z.; Le, X.; Li, X.; Zhang, W.; Dong, C.; Ma, J. Appl. Catal., B, 2014, 158-159,
129-135.
40 Le, X.; Dong, Z.; Zhang, W.; Li, X.; Ma, J. J. Mol. Catal. A: Chem., 2014, 395, 58-
65.
41 Sadeghzadeh, S.M.; Zhiani, R.; Khoobi, M.; Emrani, S. Microporous Mesoporous
Mater., 2018, 257, 147-153.
42 Nale, D.B.;Rana, S.;Parida, K.;Bhanage, B.M. Appl. Catal., A, 2014, 469, 340-349.
43 Watile, R.A.;Bhanage, B.M. Indian J. Chem.,2012, 51, 1354-1360.
44 Du, Y.; Wu, Y.; Liu, A.H.; He, L.N. J. Org. Chem., 2008, 73, 4709-4712.
45 Wu, Y.; He, L.N.; Du, Y.; Wang, J.Q.; Miao, C.X.; Li, W. Tetrahedron, 2009, 65, 6204-6210.
46 Yang, Z.Z.; He, L.N.;Peng, S.Y.; Liu, A.H. Green Chem.,2010, 12, 1850-1854.
47 Song, Q.W.; Yu, B.; Li, X.D.; Ma, R.;Diao, Z.F.; Li, R.G.; Li, W.; He, L.N. Green Chem.,
2014, 16, 1633-1638.
48 Wang, M.Y.; Song, Q.W.; Ma, R.;Xie, J.N.; He, L.N. Green Chem., 2016, 18, 282-287.
49 Sun, J.; Ren, J.; Zhang, S.; Cheng, W. Tetrahedron Lett,, 2009, 50, 423-426.
50 Lan, D.-H.; Chen, L.; Au, C.-T.; Yin, S.-F. Carbon 2015, 93, 22-31.
51 Xiao, L.; Su, D.; Yue, C.; Wu, W. J. CO2Utiliz. 2014, 6, 1-6.
9

52 Mirabaud, A.; Mulatier, J.C.; Martinez, A.; Dutasta, J.P.; Dufaud, V. ACS Catal., 2015, 5,
6748-6752.
53 Mizuno, T.; Iwai, T.; Ishino, Y. Tetrahedron Lett., 2004, 45, 7073-7075.
54 Patil, Y. P.; Tambade, P. J.; Jagtap, S. R.; Bhanage, B. M. Green Chem. Lett. Rev. 2008, 1,
127-132.
55 Patil, Y. P.; Tambade, P. J.; Deshmukh, K. M.; Bhanage, B. M. Catal. Today, 2009, 148, 355-
360.
56 Patil, Y. P.; Tambade, P. J.; Parghi, K. D.; Jayaram, R. V.; Bhanage, B. M. Catal. Lett., 2009,
133, 201-208.
57 Gao, J.; He, L. N.; Miao, C. X.; Chanfreau, S. Tetrahedron, 2010, 66, 4063-4067.
58 Jiarong, L.; Xian, C.; Daxin, S.; Shuling, M.; Qing, L.; Qi, Z.; Jianhong, T. Org. Lett.,
2009, 11, 1193-1196.
Table 1Optimization of the reaction conditions for the syntheses of Compound 1, 2, 3, and 4 in terms
of temperature, CO2 pressure, catalyst amount, time, and product yield
Entry
CO2
Temp. Time Amount
Yield (%)a
pressure
(◦C)
(min)
catalyst
(g)
Compound Compound Compound Compound
(MPa)
1
2
3
4
1
2
3
4
5
6
7
8
2
2
2
2
2
2
2
2
120
120
120
120
100
80
140
140
140
140
140
140
140
140
0.3
0.5
0.7
0.9
0.7
0.7
0.7
0.7
61
82
95
95
95
95
95
95
23
55
94
94
94
94
54
22
42
50
97
97
97
73
56
25
50
68
93
93
93
93
82
58
60
40
10

9
1.5
1
100
100
100
100
100
100
140
140
140
120
100
80
0.7
0.7
0.7
0.7
0.7
0.7
95
95
95
95
95
95
94
94
32
94
79
62
97
97
49
97
97
97
93
79
28
93
93
93
10
11
12
13
14
0.5
1.5
1.5
1.5
a Isolated yields.
Table 2The impacts of different catalysts for the syntheses of Compounds 1-4a
Entry
Catalyst
Yield (%)b
Compound 1
Compound 2
Compound 3
Compound 4
1
2
3
4
5
KCC-1
KCC-1-NH2
TPP
-
-
-
-
-
-
-
-
-
-
-
-
KCC-1/ATPP
SiO2/ATPP
95
65
94
52
97
39
93
48
aReaction conditions: aziridine, propargyl alcohol, epoxide, or 2-aminobenzonitrile (1 mmol), catalyst
(3mg), CO2, 2 MPa at 100 oC in 180 min.
bIsolated yield.
Table3The syntheses of 5-aryl-2-oxazolidinone derivatives catalyzed by KCC-1/ATPP NPsa
Entry
R1
H
Compound
Yield (%)b
1
2
3
1a
1b
1c
95
93
96
CH3
CH2CH3
11

4
5
CH2CH2CH3
1d
1e
92
97
CH2CH2CH2CH3
aReaction condition: aziridine derivatives (1 mmol), KCC-1/ATPP NPs (0.7 mg), CO2 0.5 MPa at
room temperature in 30 min.
bYield refers to isolated product.
Table 4: The syntheses of α-alkylidene CC derivatives catalyzed by KCC-1/ATPP NPsa
Entry
R1
H
R2
CH3
Compound
Yield (%)b
1
2
3
4
2a
2b
2c
2d
94
90
92
89
H
CH2CH3
Ph
H
Ph
CH3
aReaction condition: propargyl alcohol derivatives (1 mmol), KCC-1/ATPP NPs (0.7 mg), CO2 1 Mpa
at 80 oC in 120 min.
bYield refers to isolated product.
Table 5The syntheses of CC derivatives catalyzed by KCC-1/STPP NPsa
Entry
R
Compound
Yield (%)b
1
2
3
4
5
6
Me
3a
3b
3c
3d
3e
3f
97
90
92
89
83
94
Ph
4-ClC6H4
4-BrC6H4
HOCH2
ClCH2
12

7
8
PhOCH2
Bun
3g
3h
3i
88
91
93
91
86
94
9
Octn
10
11
12
4-MeC6H4
4-MeSC6H4
Et
3j
3k
3l
aReaction condition: epoxide derivatives (1 mmol), KCC-1/ATPP NPs(0.7 mg), CO2 1 MPa at 100 oC
in 100 min.
bYield refers to isolated product.
Table 6The syntheses of quinazoline-2,4(1H,3H)-dione derivatives catalyzed by KCC-1/STPP NPs
Entry
R
H
Compound
Yield (%)
1
2
3
4
5
6
4a
4b
4c
4d
4e
4f
93
95
90
94
89
91
Br
F
Cl
Me
NO2
aReaction condition: 2-aminobenzonitrile (1 mmol), KCC-1/ATPP NPs(0.7 mg), CO2 1.5 MPa at 50
oC in 70 min.
bYield refers to isolated product.
Table7A comparison of the catalytic efficiency of KCC-1/STPP NPs with various catalysts for the
synthesis of 5-aryl-2-oxazolidinone
13

Entry
Catalyst
MPa
Solvent Temperature
(CO)
Amount
Catalyst
Time
Yield (%)
(CO2)
1
2
Amine@MCM-41
CSHB
5
5
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
6
6
6
6
6
-
40
70
25 wt%
8 h
7 h
92[42]
61[43]
-
20 wt%
[44]
3
PEG6000
-
100
100
100
100
40
0.8 mol (%)
0.8 mol (%)
0.8 mol (%)
0.8 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
20 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
5 min
5 min
5 min
5 min
4 h
-
4
Bu4NBr
-
6[44]
38[44]
71[44]
30[45]
31[45]
22[45]
1[45]
5
Bu4NBr/PEG6000
PEG6000(NBu3Br)2
I2
-
6
-
7
CH2Cl2
8
LiBr
CH2Cl2
40
4 h
9
AlCl3
CH2Cl2
40
4 h
10
11
12
13
14
15
16
17
18
19
20
21
22
ZnCl2
CH2Cl2
40
4 h
Morpholine
ZrOCl2.8H2O
DMAP
-
40
4 h
3[45]
-
40
4 h
41[45]
1[45]
-
40
4 h
DBN
-
40
4 h
0.4[45]
[45]
DBU
-
40
4 h
-
[45]
DABCO
CH2Cl2
40
4 h
-
[45]
HMTA
CH2Cl2
40
4 h
-
[C4DABCO]Br
[C4DABCO]OH
[C4DABCO]Cl
[C8DABCO]Br
[C8DABCO]BF4
-
-
-
-
-
90
3 h
85[46]
56[46]
43[46]
75[46]
26[46]
90
3 h
90
3 h
90
3 h
90
3 h
14

23
24
25
26
27
28
[C8DABCO]PF6
[C8DABCO]NTf2
[C12DABCO]Br
[C4MIm]Br
6
6
-
-
-
-
-
-
90
90
90
90
90
r.t.
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
0.4 mol (%)
3 h
3 h
19[46]
11[46]
70[46]
76[46]
14[46]
95
6
3 h
6
3 h
[C4MIm]BF4
6
3 h
KCC-1/ATPP
0.5
30 min
aReaction conditions: aziridine (1 mmol), and CO2 in different solvents and in different amounts of
catalyst, temperature, and time.
Table8A comparison of the catalytic efficiency of KCC-1/STPP NPs with various catalysts for the
synthesis of α-alkylidene CC
Entry
Catalyst
MPa Solvent Temperature
Amount
Catalyst
Time
Yield
(%)
(CO)
(CO2)
[47]
1
2
DBU
Ph3P
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
-
-
-
-
-
-
-
-
-
-
-
-
50
50
50
50
50
50
40
40
40
40
60
60
2 mol (%)
2 mol (%)
2 mol (%)
2 mol (%)
2 mol (%)
2 mol (%)
2 mol (%)
2 mol (%)
2 mol (%)
2 mol (%)
6 h
6 h
6 h
6 h
6 h
6 h
6 h
6 h
6 h
6 h
-
[47]
-
[47]
3
CuCl
-
[47]
4
AgNO3/Ph3P
AgOAc/Ph3P
Ag2WO4/Ph3P
AgI/Ph3P
-
5
<1[47]
45[47]
6
[47]
7
-
8
Ag2WO4/DBU
Ag2WO4/2,2-Bipyridine
Ag2WO4/TMEDA
(nC7H15)4NBr
K8[α-SiW11O39]
2[47]
[47]
9
-
[47]
10
11
12
-
[48]
2.5 mol (%) 20 h
2.5 mol (%) 20 h
-
[48]
-
15

13
14
15
16
17
18
19
20
21
K6[SiW11O39Cu]
CuCl2
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1
-
-
-
-
-
-
-
-
-
60
60
60
60
60
60
60
60
80
2.5 mol (%) 20 h
2.5 mol (%) 20 h
2.5 mol (%) 20 h
2.5 mol (%) 20 h
2.5 mol (%) 20 h
2.5 mol (%) 20 h
2.5 mol (%) 20 h
2.5 mol (%) 20 h
43[48]
67[48]
68[48]
66[48]
18[48]
16[48]
45[48]
43[48]
94
CuCl2+(nC7H15)4NBr
[(nC7H15)4N]6[α-SiW11O39Co]
[(nC7H15)4N]6[α-SiW11O39Fe]
[(nC7H15)4N]6[α-SiW11O39Ni]
[(nC7H15)4N]6[α-SiW11O39Zn]
[(nC7H15)4N]6[α-SiW11O39Mn]
KCC-1/ATPP
0.4 mol (%)
2 h
aReaction conditions: propargyl alcohol (1 mmol), and CO2 in different solvents and in different
amounts of catalyst, temperature, and time.
Table9A Comparison of the catalytic efficiency of KCC-1/STPP NPs with various catalysts for the
synthesis of CC
Entry
Catalyst
MPa Solvent Temperature
Amount
Catalyst
Time Yield
(CO)
(h)
(%)
(CO2)
1
2
3
4
5
6
7
8
9
NaBr
KBr
2
2
2
2
2
2
2
2
2
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
125
125
125
125
125
125
125
125
125
1 mmol
1 mmol
1 mmol
1 mmol
1 mmol
1 mmol
1 mmol
1 mmol
1 mmol
1
1
1
1
1
1
1
1
1
30[49]
52[49]
68[49]
86[49]
46[49]
88[49]
87[49]
42[49]
90[49]
KI
Bu4NBr
Bu4NCl
Bu4NI
[bmim]Br
[bmim]Cl
[bmim]I
16

10
11
12
13
14
15
16
17
18
19
20
21
GO-DMEDA-I
Mim
2
-
-
-
-
-
-
-
-
-
-
-
-
120
120
120
120
120
120
120
120
100
100
100
100
0.65 mol (%)
1 mol (%)
1 mol (%)
0.5 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
1 mol (%)
0.4 mol (%)
3
2
89[50]
[51]
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1
-
HBimBr
2
77.7[51]
59.8[51]
85.8[51]
47.4[51]
31.6[51]
34.9[51]
63[52]
HMimBr
HEimBr
2
2
HMimCl
2
HPyBr
2
HTeaBr
2
Et4N+Cl–
24
24
24
1.7
n-Bu4N+Cl–
n-Bu3MeN+Cl–
KCC-1/ATPP
1
61[52]
1
58[52]
1
97
aReaction conditions: epoxide (1 mmol), CO2 in different solvents associated with different catalyst amounts, temperatures, and times
Table10A comparison of the catalytic efficiency of KCC-1/STPP NPs with various catalysts for the
synthesis of quinazoline-2,4(1H,3H)-dione
Entry
Catalyst
MPa(CO2) Solvent
Temperature
(CO)
Amount
Catalyst
Time
(h)
Yield
(%)
[55]
1
2
3
4
5
6
7
-
3
3
3
3
3
3
3
-
-
-
-
-
-
-
120
120
120
120
120
120
120
-
18
18
18
18
18
18
18
-
Cs2CO3
t-BuOK
KF
5 mol (%)
5 mol (%)
5 mol (%)
5 mol (%)
5 mol (%)
-
10[55]
[55]
-
5[55]
Et3N
28[55]
[55]
[Bmim]BF4
[Bmim]HSO4
-
[55]
-
17

8
[Bmim]OH
TMG
3
10
3.7
5
-
120
120
130
200
200
200
200
200
200
200
100
100
100
100
100
80
10 mol (%)
5 mol (%)
10 mol (%)
1 equiv
18
4
91[55]
89[57]
92[57]
20[56]
15[58]
9
-
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
MgO/ZrO2
CuCl2
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
-
12
5
HgCl2
5
1 equiv
5
[58]
FeCl3
5
1 equiv
5
-
[58]
AlCl3
5
1 equiv
5
-
[58]
SnCl2
5
1 equiv
5
-
TiCl4
5
1 equiv
5
2[58]
90[58]
35[54]
0[54]
ZnCl2
5
5 equiv
5
K2CO3
Na2CO3
KF
1.3
1.3
1.3
1.3
1.3
10
1.5
0.25 equiv
0.25 equiv
0.25 equiv
0.25 equiv
0.25 equiv
0.1equiv
0.4 mol (%)
4
4
4
40[54]
55[54]
94[54]
91[53]
93
KOH
4
Cs2CO3
DBU
4
4
KCC-1/ATPP
-
50
1.2
aReaction conditions: 2-aminobenzonitrile (1 mmol), and CO2 in different solvents and in different
amounts of catalyst, temperature, and time.
18

O
R1
O
N
O
O
O
Compound 3
Compound 1
Me
O
R1
N
Me
O
O
O
Si
+H3N
O-
O
O
O
SiO
O
O
OSi
O
+-O P O P O P O-+
NH3
H3N
CO2
O- + O
NH3
O-
NH3
+
KCC-1/ATPP
Si
Si
KCC-1 Fiber
O
O
O
O
O
O
Me
OH
Me
NH2
CN
O
H
N
O
O
O
NH
O
Compound 4
Compound 2
Scheme 1: CO2 transformation in the presence of KCC-1/STPP NPs
19

O
O
O
Si
EtO
EtO Si
EtO
NH2
+
NH2
KCC-1
O-
O
O-
-O P O P O P O-
O
O-
O
O
Si
O
O
O
O
O
Si
+H3N
O-
O-
O
O-
O
O
O
O
OSi
O
-O P O P O P O-
+
+
-O P O P O P O-
+H3N
O
Si
NH3
NH3
O-
O
O-
NH3
O
O
O-
O
+
+
NH3
KCC-1/ATPP
Si
O
Si
O
KCC-1 Fiber
O
O
O
O
Scheme 2: Schematic illustration of the synthesis of KCC-1/ATPP NPs
O
R1
R1
N
O
N
+
CO2
Ph
Ph
1a-e
Scheme 3Carboxylative cyclization of various aziridines with CO2.
O
R2
OH
Me
O
+
CO2
R1
O
R1
Me
R2
2 a-d
Scheme 4Carboxylative cyclization of propargyl alcohols with CO2
20

O
O
O
O
CO2
+
R
R
3 a-l
Scheme5The synthesis of CCs in the presence of KCC-1/STPP NPs
H
NH2
N
O
CO2
+
NH
R
CN
R
O
4 a-f
Scheme6The syntheses of quinazoline-2,4(1H,3H)-diones in the presence of KCC-1/STPP NPs
21