Fe3O4?SiO2?(BuSO3H)3 synthesis as a new efficient nanocatalyst and its application in the synthesis of heterocyclic [3.3.3] propellane derivatives

Article abstract of DOI:10.1016/j.poly.2019.114343

The acidic agent (BuSO₃H) coated on core‐shell Fe₃O₄ nanomagnetic particles was successfully designed and synthesized. It was characterized and confirmed by different techniques such as FT‐IR spectroscopy, scanning electron microscopy vibrating sample magnetometer, X‐Ray diffraction, energy dispersive X-ray and Thermogravimetric analysis. The application of Fe₃O₄?SiO₂?(BuSO₃H)₃ as an efficient catalyst in the synthesis of propellane derivatives was evaluated by the domino reaction of acenaphthenequinone, malono derivatives, primary amines and β-ketoester derivatives under the solvent-free condition at 60 °C.

Full text of DOI:10.1016/j.poly.2019.114343

Journal Pre-proofs
Fe O @SiO @(BuSO H) Synthesis as a new efficient nanocatalyst and its ap-
3
4
2
3
3
plication in the synthesis of heterocyclic [3.3.3] propellane derivatives
Zohreh Kheilkordi, Ghodsi Mohammadi Ziarani, Alireza Badiei
PII:
S0277-5387(19)30788-0
DOI:
https://doi.org/10.1016/j.poly.2019.114343
POLY 114343
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
24 September 2019
28 December 2019
30 December 2019
Please cite this article as: Z. Kheilkordi, G. Mohammadi Ziarani, A. Badiei, Fe O @SiO @(BuSO H) Synthesis
3
4
2
3
3
as a new efficient nanocatalyst and its application in the synthesis of heterocyclic [3.3.3] propellane derivatives,
Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.2019.114343
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Fe O @SiO @(BuSO H) Synthesis as a new efficient nanocatalyst and its application in
3
4
2
3
3
the synthesis of heterocyclic [3.3.3] propellane derivatives
1
1
2
Zohreh Kheilkordi , Ghodsi Mohammadi Ziarani *, Alireza Badiei
1
Department of Chemistry, Alzahra University, Vanak Square, Tehran, Iran
2
School of Chemistry, College of Science, University of Tehran, Tehran, Iran
*Corresponding Email Address: gmohammadi@alzahra.ac.ir
Abstract
The acidic agent (BuSO H) coated on core‐shell Fe O nanomagnetic particles was
3
3
4
successfully designed and synthesized. It was characterized and confirmed by different
techniques such as FT‐IR spectroscopy, scanning electron microscopy vibrating sample
magnetometer, X‐Ray diffraction, energy dispersive X-ray and Thermogravimetric analysis. The
application of Fe O @SiO @(BuSO H) as an efficient catalyst in the synthesis of propellane
3
4
2
3
3
derivatives was evaluated by the domino reaction of acenaphthenequinone, malono derivatives,
°
primary amines and β-ketoester derivatives under the solvent-free condition at 60 C.
Keywords: Magnetic nanocatalyst, Fe O @SiO @(BuSO H) , [3.3.3] Propellane, Domino
3
4
2
3
3
reaction, Multicomponent reaction
1
. Introduction
In recent years, the use of green chemistry rules including reduction of by-product and
waste, reducing energy utilization, application of solvent-free conditions and the use of non-toxic
stating materials is more important [1-3]. The application of hybrid organic and inorganic
materials as heterogeneous catalysts in chemistry is one of the advantages of green chemistry.
Recently, among various heterogeneous catalysts, the modification of Fe O nanoparticles with
3
4
organic and inorganic compounds attracted very attention [4-6]. Fe O nanoparticles have special
3
4
properties including easy synthesis, low cost, nontoxicity, high stability, easy separation by
external magnetic and high surface‐area [7,8]. Fe O nanoparticles were applied in different
3
4
fields such as sensor, drug delivery, and as a catalyst in the multicomponent reaction [9-11]. So,
we decided to use the Fe O nanoparticle as a magnetic core, and then it was modified by organic
3
4
1

and inorganic reagents to creat the Fe O @SiO @(BuSO H) as an efficient nanomagnetic
3
4
2
3
3
catalyst.
In the 1930s during studies on the Diels–Alder reaction, the first propellanes were prepared [12-
4]. Among the organic compounds, propellane compounds have tricyclic structure whit a C-C
1
band in common in three rings (Scheme 1) [15]. According to scheme 1, when (n) in the
structure is equal to one, three-membered rings under angular pressure are formed [16].
Propellanes, due to their presence in the different structure including natural and unnatural
products, medicinal compounds and polymers were attracted many attentions in nowadays [17].
(
CH )n
2
(
CH )n
2
n(H C)
2
1
Scheme 1. The general structure of propellane.
As shown in Scheme 2, propellane derivatives exist in a great part of the natural compound
structures such as Periglaucinc A [18], Hasubanone alkaloids [19], Sinoacutine [20],
Hasubanan[21] and Merrilactone A [22]
O
OMe
MeO
HO
O
OMe
NH
HO
O
O
O
H
N
O
N
Me
OMe
O
O
OMe
O
Me
N
Me
O
OMe
Me
O
OMe
Periglaucinc A
Hasubanone
Sinoacutine
Hasubanan
Merrillactone A
Scheme 2. Typical natural products with propellane skeleton.
Therefore, according to the green chemistry roles, multi-component reactions, are a useful
method in medicinally, pharmacologically and chemistry science [23-24]. Subsequently, they
were applied in the synthesis of biological and pharmacological compounds because this method
is green and eco-friendly [25-27]. Recently, the synthesis of propellane compounds became very
interesting for many researchers [18, 28-31]. Therefore, according to our previous research in the
context of multicomponent reactions [32-39], in this work, it is reported the efficient, green, eco-
friendly and simple method for synthesis of [3.3.3] propellane derivatives via domino reaction of
2

acenaphthoquinone, malononitrile, β-keto ester and anilines under solvent condition in the
°
presence of Fe O @SiO @(BuSO H) at 60 C. The advantages of this work are including green
3
4
2
3
3
conditions, the use of available materials, the high yield products, the low reaction times, the
simple purification, the easy separation of catalyst from mixture reaction by an external magnet
and the reusability of catalyst.
2
. Experimental
All material and methods were introduced in the supporting information. Nanomagnetic particles
Fe O , Fe O @SiO , Fe O @SiO Pr-NH(CH ) NH were obtained according to the reported
3
4
3
4
2
3
4
2
2 2
2
articles in literature [40- 42].
.1. Synthesis of Fe O @SiO @(BuSO H)
For the synthesis of nanomagnetic catalyst, the mixture of Fe O @SiO (CH ) NH(CH ) NH (1
2
3
4
2
3
3
3
4
2
2 3
2 2
2
gr) and dry toluene (25 ml) was sonicated for 1 h, and then 1,4‐butane sultone (5 ml) was added
to this colloidal solution. The reaction mixture was refluxed for 36 h, and then, the nanomagnetic
catalyst separated by an external magnet, and washed with dichloromethane, and dried at room
temperature.
2
.2.
General procedure for the synthesis of [3.3.3] propellane
For the synthesis of [3,3,3] propylene, initially, acenaphtoqinone (1.0 mmol, 0.16 gr) and
malononitrile (1 mmol, 0.66 gr) in the presence of Fe O @SiO @(BuSO H) (0.01 gr) under
3
4
2
3
3
°
solvent-free conditions were stirred at 60 C for ten minutes. Afterward, 4-Cl-aniline (1 mmol,
0
.12 gr) and β-ketoester (1 mmol, 0.12 ml) were added the mixture reaction and the reaction
°
continued under solvent-free conditions at 60 C. The progression of the reaction was followed
by TLC using ethyl acetate: hexane (8: 2) ratio as solvent. After completion of the reaction, the
reaction mixture was dissolved in hot ethanol, and then the nano magnetic catalyst separated
using an external magnet from the aqueous solution, and then, The pure sediment of the product
was obtained. The obtained products were characterized using melting point and FT‐IR spectra
1
13
and the new compounds were charecterizied by the H and C NMR spectra.
1
.
Ethyl (6bR,9aR)-11-amino- 7-(4-bromophenyl)-10 -cyano-8-methyl-7H-6b,9a-
(epoxyetheno) acenaphtho [1,2-b]pyrrole-9-carboxylate (6g)
3

-1
White solid; m.p. 216-218 ˚C; IR (KBr, ν, cm ): 3467, 3316, 3255, 3195, 3056, 2978, 2931,
2
9
196, 1680, 1658, 1598, 1489, 1423, 1381, 1323, 1252, 1236, 1198, 1130, 1092, 1069, 1010,
1
54, 830 and 809. H NMR (500 MHz, DMSO-d ): δ (ppm)= 1.44-146 (t, 3H, Me), 2.09 (s, 3H,
6
Me), 4.22-4.37 (m, 2H, CH ), 6.52-6.53 (d, 1 H, Ar), 7.26-7.27 (d, 1H, Ar), 7.30 (s, 2H, NH ),
2
2
7
7
7
1
2
.39-7.42 (t, 1H, Ar), 7.64-7.66 (t, 1H, Ar), 7.71-7.73 (d, 2H, Ar), 7.78-7.79 (d, 1H, Ar), 7.84-
1
3
.86 (t, 2H, Ar). ). C NMR (125 MHz, DMSO-d ): δ (ppm)= 13.96, 14.93, 59.43, 59.49,
6
0.88, 106.38, 114.91, 119.16, 119.70, 120.51, 121.66, 124.10, 126.71, 128.32, 129.47, 131.13,
32.20, 133.00, 136.24, 136.71, 136.80, 144.49, 157.39, 166.22, 167.88.
. Ethyl (6bR,9aR)-11- amino -10- cyano-8-methyl-7- phenyl- 7H-6b,9a- (epoxyetheno)
acenaphtho [1,2-b] pyrrole-9-carboxylate (6h)
-1
White solid; m.p. 202-204 ˚C; IR (KBr, ν, cm ): 3420, 3306, 3192, 3062, 2978, 2931, 2182,
1
1
657, 1634, 1592, 1487, 1494, 1456, 1423, 1399, 1382, 1367, 1339, 1260, 1233, 1199, 1146,
1
122, 1087, 1066, 1007, 950, 928, 885, 728 and 757. H NMR (500 MHz, DMSO-d ): δ
6
(
ppm)= 1.43-1.46 (t, 3H, Me), 2.09 (s, 3H, Me), 4.22-4.37 (m, 2H, CH ), 6.39-6.40 (d, 1H, Ar),
2
7
.27 (s, 2H, NH ), 7.34-7.37 (t, 1H, Ar), 7.47-7.54 (m, 3H, Ar), 7.62-7.66 (t, 1 H, Ar), 7.78-7.80
2
1
3
(
d, 1H, Ar), 7.83-7.87 (m, 2H, Ar). ). C NMR (125 MHz, DMSO-d ): δ (ppm)= 14.02, 14.06,
6
5
1
9.39, 59.48, 70.75, 106.82, 115.16, 119.26, 119.66, 120.47, 124.02, 126.58, 128.07, 128.77,
29.22, 129.43, 130.00, 132.18, 136.76, 136.84, 136.97, 144.70, 157.80, 166.29, 167.94.
3
. Results and discussion
.1. Preparation of catalyst
3
Nanomagnetic particles Fe O were obtained from the reaction of FeCl ·6H O, FeCl 4H O
3
4
3
2
2.
2
and ammonia solution (25%) in the water at in 100 °C under nitrogen atmosphere. After core-
shell structure of nanomagnetic particles were synthesized by tetraethyl orthosilicate in room
temperature. Afterward, the core-shell structure (Fe O @SiO ) was modified by N-(3-
3
4
2
triethoxysilylpropyl)ethylenediamine. In the next step, the amine groups on the surface of
magnetic nanoparticles were functionalized by 1,4-butane saltone and finally, the nanocatalyst
was prepared (Scheme 3).
4

NH2
O
NH
Si
O
O
FeCl .4H O
2
2
NH (25%)
TEOS
3
Fe3O4
3 4
Fe O
+
Reflux toluene (dry)
24 h
N2
r.t., 20 h
SiO2
FeCl .6H O
3
2
SO H
3
O
O
O
S O
NH2
O
N
Si
N
Si
N
SO H
3
H
O
Fe3O4
SiO2
O
Fe3O4
SiO2
O
O
Reflux toluene (dry)
6 h
3
SO H
3
Scheme 3. Synthesis of Fe O @SiO @(BuSO H) .
3
4
2
3
3
3
3
.2.
Characterization of the catalyst
.1.1. FT-IR analysis
The FT‐IR spectra of the Fe O , Fe O @SiO , Fe O @SiO @PrNH(CH ) NH and
3
4
3
4
2
3
4
2
2 2
2
-1
Fe O @SiO @(BuSO H) were shown in Figure 1. All bands at around 574 cm are ascribed to
3
4
2
3
3
-1
Fe-O vibrations. The weak bands at around 800 cm related to the SiO groups. The strong
4
-1
absorbent bands around the area 1080 cm , were attributed to the Si-O-Si groups. The absorbent
-1
peak in the 2931 cm was indicated the C–H stretching vibrations of alkyl groups. The broad
-1
peak in the 3442 cm was related to the various groups including SO H and OH agent in the
3
silica shell.
5

Fig. 1. FT‐IR spectra of Fe O (a), Fe O @SiO (b), Fe O @SiO @Pr-NH(CH ) NH (c) and
3
4
3
4
2
3
4
2
2 2
2
Fe O @SiO @(BuSO H)
3
3
4
2
3
3
.1.2. XRD analysis
As shown in Figure 2, the X-ray diffraction (XRD) pattern of Fe O (a) and
3
4
°
°
°
°
Fe O @SiO @BSH (b) were displayed. The various peaks at 2θ= 18 , 30.12 , 35.56 , 43.26 ,
3
4
2
°
°
°,
°
5
3.56 , 57.24 , 62.8 and 74.34 , correspond to the different planes including (111), (220), (311),
(
400), (422), (511), (440) and (622). According to Figure 2, both nanoparticles including Fe O
3
4
and Fe O @SiO @(BuSO H) have the same pattern which demonstrates the successful
3
4
2
3
3
nanoparticles synthesis.
6

Fig. 2. XRD pattern of Fe O and Fe O @SiO @(BuSO H) .
3
4
3
4
2
3
3
3
.1.3. Energy Dispersive X-ray Spectroscopy (EDX) analysis
The EDX spectrum of the Fe O @SiO @(BuSO H) showed in Figure 3. The presence of
3
4
2
3
3
different elements, including C, N, O, Si, S, Fe was demonstrated in the
Fe O @SiO @(BuSO H) nanocatalyst. According to Figure 4, the SEM image of the
3
4
2
3
3
Fe O @SiO @(BuSO H) nanoparticles are spherical with average size 60-80 nm.
3
4
2
3
3
Fig. 3. EDX spectrum of Fe O @SiO @BSH.
3
4
2
7

Fig. 4. SEM image of Fe O @SiO @(BuSO H)
3.
3
4
2
3
3
.1.4. Thermogravimetric analysis (TGA)
The thermogravimetric analysis was investigated for Fe O @SiO @Pr-NH(CH ) NH and
3
4
2
2 2
2
°
Fe O @SiO @(BuSO H) catalyst at the room temperature to 1000 C under air atmosphere. As
3
4
2
3
3
°
shown in Figure 4, the weight loss of 7 % and 9 % in the range 20-200 C related to the loss of
the adsorbed water on the surface of Fe O @SiO @Pr-NH(CH ) NH and
Fe O @SiO @(BuSO H) respectively. According to Figure 5, with the increase of the
3
4
2
2 2
2
3
4
2
3
3
hydrophilic group (SO H) on the surface of the nanocatalyst, the surface water percentage was
3
increased. Also, the weight loss of organic part in the nanoparticles in the range of 200-550 °C is
around 8.5 % and 17.5 % for Fe O @SiO @Pr-NH(CH ) NH and Fe O @SiO @(BuSO H)
3.
3
4
2
2 2
2
3
4
2
3
-1
The amount of the grafted organic compound was evaluated to be about 0.60 mmol g .
8

Fig. 5. Thermogravimetric analysis of a) Fe O @SiO @Pr-NH(CH ) NH and b)
3
4
2
2 2
2
Fe O @SiO @(BuSO H)
3
4
2
3
3
3
.1.5. Magnetic properties of nanomagnetic particles (VSM)
The magnetic properties of nanoparticles including Fe O , Fe O @SiO
and
Fe O @SiO @(BuSO H) were investigated by vibrating sample magnetometer (VSM) at room
3
4
3
4
2,
3
4
2
3
3
temperature. As shown in Figure 6, the magnetization behavior of Fe O , Fe O @SiO and
3
4
3
4
2,
Fe O @SiO @(BuSO H) is respectively equal to 60 emu/gr, 48 emu/gr, and 33 emu/gr.
3
4
2
3
3
9

Fig. 6. Magnetization curves of a) Fe O , b) Fe O @SiO and c) Fe O @SiO @(BuSO H)
3
3
4
3
4
2,
3
4
2
3
3
.3.
Synthesis of [3.3.3] propellane by Fe O @SiO @(BuSO H) as a catalyst
3 4 2 3 3
Initially, the catalytic activity of the Fe O @SiO @(BuSO H) nanoparticles was studied in the
3
4
2
3
3
reaction model for the synthesis of [3.3.3] propellane 5a (Scheme 4). Various conditions
including solvent-free systems, reflux in EtOH, H O, H O: EtOH (1:1) and without catalyst were
2
2
studied. As shown in Table 1, among different conditions, the best results were obtained under
°
domino reaction and solvent-free condition at 60 C in the presence of Fe O @SiO @(BuSO H)
3
4
2
3
3
catalyst.
Cl
CN
CN NH2
O
O
O
O
O
O
N
CN Condition
CN
Condition
+
+
+
OEt
NH2
Cl
O
CN
O
1
2
6
3
4
5
Scheme 4. Synthesis [3.3.3]propellane 5a as a model of reaction
1
0

Table 1 The reaction conditions optimization in the synthesis of [3.3.3] propellane 5a.
Entry
Catalyst (gr)
Solvent
-
Condition
rt.
Time (h)
Yield (%)
1
2
3
4
5
6
7
-
5
4
-
Fe O @SiO @BSH (0.01gr)
EtOH
Reflux
Reflux
Reflux
60 °C
70
40
55
91
92
70
3
4
2
Fe O @SiO @BSH (0.01 gr)
H O
2
6
3
4
2
Fe O @SiO @BSH (0.01 gr)
EtOH:H O (1:1)
4
3
4
2
2
Fe O @SiO @BSH (0.08 gr)
-
-
-
55 min
40 min
40 min
3
4
2
Fe O @SiO @BSH (0.01 gr)
60 °C
3
4
2
Fe O @SiO @BSH (0.01 gr)
90 °C
3
4
2
In order to further study of catalytic activity Fe O @SiO @(BuSO H) nanoparticles in this
3
4
2
3
3
work, various [3.3.3] propellane derivatives were synthesized successfully under the solvent‐free
condition in 60 °C (Scheme 5). According to the obtained results in table 2, all products were
synthesized in a short time and excellent yield. The structure of new products was determined by
1
13
melting point, IR, H NMR, and C NMR spectra.
NC
O
CN
O
O
SO3
H
SO3H
R1
O
N
O
N
Si
N
SO3H
Si
N
SO3H
O
O
Fe3O4
O
Fe3O4
SiO2
O
6
O
N
R2
1
SiO2
SO3H
SO3H
+
NH2
Solvent free, 60 o
C
Solvent free, 60 o
+
C
O
NC CN
R1
H2N
CN
O
O
O
2
R2
OEt
5
3
4
Scheme 5. Synthesis [3.3.3] propellane derivatives 5a-h.
Table 2 The synthesis of [3.3.3] propellane derivatives 5a-h.
R1
R2
Time (min)
°
°
Entry
Yield (%) m.p. ( C) m.p. ( C) [Ref.]
1
2
3
4
5
4-Cl C H
Me
40
35
30
30
35
90
91
93
93
92
245-247
232-234
247-250
248-250
250-252
251-253 [28]
247-249 [28]
250-252 [28]
247-249 [28]
249-251 [28]
6
4
Benzyl
Et
C H
6
5
Me
Me
Me
Butyl
Benzyl
1
1

6
7
4-BrC H
Me
Me
40
35
91
93
216-218
202-204
New
New
6
4
C H
6
5
The plausible mechanism for synthesis of [3.3.3] propellane 5a in the presence of
Fe O @SiO @(BuSO H) as a catalyst was shown in (Scheme 6). Malononitrile 2 attacks to the
3
4
2
3
3
carbonyl group of acenaphthoquinone 1 via a Knoevenagel reaction to generate intermediate 6.
The nucleophilic addition 4-chloro aniline 4 to beta keto ester 3a gave intermediate 7 which was
reacted with intermediate 6 via Michael addition to produce intermediate 8. Via proton transfer,
the compound 8 was converted to the intermediate 9, which produced propellane 5a
subsequently via the intramolecular cyclization attack of the nitrogen atom, the intramolecular
O-cyclization, and then tautomerization.
O
O
O
S
O
S
O
Cl
H
O
CN
Cl
H
NH2
O
O
O
H
NC
N
O
O
N
O
NC
NC
+
+
OEt
OEt
+
Cl
EtO
O
3a
4
7
7'
6
2
1
Cl
Cl
Cl
O
R1
O
O
O
N
O
O
S
O
O
H
HN
N
O
O
O
N
NH
O
NH2
O
OEt
OEt
NC
NH
O
CN
NC
Cl
NC
CN
N
H
OEt
N
O
CNOEt
1
1
S
O
5a
8
9
10
H
O
O
O
H
S
O
Scheme 6. Proposed mechanism for the synthesis of [3.3.3] propellane 5a.
The recyclability of Fe O @SiO @(BuSO H) nanoparticles was measured in the synthesis of
3
4
2
3
3
[3.3.3]propellan 5a under the optimized conditions. Therefore, the nanocatalyst was washed
several times with hot ethanol, distilled water, and diluted sulfonic acid solution. Then the
nanocatalyst dried at room temperature. As showed in table 3, Fe O @SiO @(BuSO H) was
3
4
2
3
3
reused four times for model reaction.
Table 3 Recyclability of Fe O @SiO @(BuSO H)
3
3
4
2
3
1
2

Entry Time (min)
Yield (%)
1
2
3
4
40
40
40
40
90
89
85
83
According to table 4, we compared the effect of Fe O @SiO @(BuSO H) with tri-ethylamine
3
4
2
3
3
(
Et N) as a catalyst as the reaction model. This work in compared with the previous method has
3
various advantages including, great yields, high purity products, shorter reaction time. One of the
most important benefits this work applied that the nanomagnetic catalyst that is easily separated
from the reaction mixture by the external magnet.
Table 4
Comparison of different conditions in the synthesis of compound 5a.
Entry
Catalyst
Solvent
EtOH
-
Condition
Time (h)
2.7
Yield (%)
77 [28]
90
1
2
Et N
3
r.t.
60
Fe O @SiO @(BuSO H)
3
40 min
3
4
2
3
4
. Conclusion
In this work, we prepared Fe O @SiO @(BuSO H) , and characterized using FT-IR, XRD,
3
4
2
3
3
TGA, VSM, SEM, and EDX analyses, and then it was used as a new nanocatalyst in the
synthesis of [3.33] propellanes. This catalyst has different advantages such as eco-friendly
efficient, green reaction conditions, short reaction times, an excellent yield of products, simple
separation of the catalyst by using external magnet from the reaction mixture.
Acknowledgments
We are grateful to the Alzahra and Tehran Universities Research Councils for their support.
References
1
3

[
[
[
[
[
[
[
[
[
[
1] L.D.S. Yadav, S. Singh, V.K. Rai, Green Chem. 11 (2009) 878.
2] W. Leitner, Green Chem, 11 (2009) 603.
3] D.B. Ramachary, M. Kishor, J. Org. Chem.72 (2007) 5056.
4] D. Astruc, F. Lu, J.R. Aranzaes, Angew. Chem. Int. Ed. 44 (2005) 7852.
5] B. Tahmasbi, A. Ghorbani-Choghamarani, Catalysis Lett. 147 (2017) 649.
6] A. Schätz, O. Reiser, W.J. Stark, Chem. Eur. J. 16 (2010) 8950.
7] J. Meurig Thomas, R. Raja, Annu. Rev. Mater. Res., 35 (2005) 315.
8] M.-J. Yao, Z. Guan, Y.-H. He, Synth. Commun. 43 (2013) 2073.
9] S. Shylesh, V. Schünemann, W.R. Thiel, Angew. Chem., Int. Ed. 49 (2010) 3428.
10] V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.-M. Basset, Chem. Rev. 111 (2011)
3
036.
[
[
[
[
[
[
11] D. Wang, D. Astruc, Chem. Rev. 114 (2014) 6949.
12] O. Diels, W. Friedrichsen, Justus Liebigs Ann. Chem. 513 (1934) 145.
13] L. Fieser, J. Dunn, J. Am. Chem. Soc. 58 (1936) 1054.
14] K. Alder, K.H. Backendorf, Ber. Dtsch. Chem. Ges. 71 (1938) 2199.
15] R.W. Weber, J.M. Cook, Can. J. Chem. 56 (1978) 189.
16] M. Shin, M.H. Kim, T.-h. Ha, J. Jeon, K.-H. Chung, J.S. Kim, Y.G. Kim, Tetrahedron, 70 (2014)
1
617.
[17] A. Ioffe, V. Svyatkin, O. Nefedov, Bull. Acad. Sci. USSR, Div. Chem. Sci. 37 (1988) 1827.
[
[
[
[
18] A. Rezvanian, A. Alizadeh, Tetrahedron, 68 (2012) 10164.
19] T. Ibuka, K. Tanaka, Y. Inubushi, Chem. Pharm. Bull. 22 (1974) 782.
20] H.-Y. Lee, D.-I. Kim, S. Kim, Chem. Comm. (1996) 1539.
21] Y. Sugimoto, H.A. Babiker, T. Saisho, T. Furumoto, S. Inanaga, M. Kato, J. Org. Chem. 66 (2001)
3
299.
22] J.-m. Huang, R. Yokoyama, C.-s. Yang, Y. Fukuyama, Merrilactone A, Tetrahedron Lett. 41 (2000)
111.
[
6
[
[
[
[
[
[
[
[
23] A. Hasaninejad, A. Zare, M. Shekouhy, Tetrahedron, 67 (2011) 390.
24] B. Maleki, G.E. Kahoo, R. Tayebee, Org. Prep. Proced. Int. 47 (2015) 461.
25] A. Shahrisa, R. Teimuri-Mofrad, M. Gholamhosseini-Nazari, synlett, 26 (2015) 1031.
26] A. Maleki, E. Akhlaghi, R. Paydar, Appl. Organomet. Chem. 30 (2016) 382.
27] A. Shahrisa, S. Esmati, Synlett, 24 (2013) 595-602.
28] M. Beyrati, A. Hasaninejad, RSC Adv. 8 (2018) 14171.
29] A. Rezvanian, A. Alizadeh, L.-G. Zhu, Synlett, 23 (2012) 2526.
30] A. Alizadeh, A. Rezvanian, L.-G. Zhu, J. Org. Chem. 77 (2012) 4385.
1
4

[
31] I. Yavari, A. Malekafzali, S. Skoulika, Tetrahedron Lett. 55 (2014) 3154.
32] G. Mohammadi Ziarani, Z. Kazemi Asl, P. Gholamzadeh, A. Badiei, M. Afshar, Inorg Nano-Met
Chem. 48 (2018) 515.
[
[
33] G. Mohammadi Ziarani, Z. Kazemi Asl, P. Gholamzadeh, A. Badiei, M. Afshar, Appl. Organomet.
Chem. 31 (2017) e3830.
[34] G.Mohammadi. Ziarani, Z.K. Asl, P. Gholamzadeh, A. Badiei, M. Afshar, J. Sol-Gel. Sci. Technol.
8
5 (2018) 103.
[
[
[
35]Z. Kheil kordi, G.Mohammdi. Ziarani, S. Bahar, A. Badiei, J. Iran. Chem. Soc. 16 (2019) 365.
36] Z. Kheilkordi, G.M. Ziarani, N. Lashgari, A. Badiei, Polyhedron, 166 (2019) 203.
37] V.Fathi Vavsari, G.M. Ziarani, S. Balalaie, A. Latifi, M. Karimi, A. Badiei, Tetrahedron, 72 (2016)
5
420.
[38] V. Fathi Vavsari, G. Mohammadi Ziarani, S. Balalaie, A. Badiei, F. Golmohammadi, S.
Ramezanpour, F. Rominger, Chem. Select, 2 (2017) 3496.
[
39] T. Ahmadi, G.M. Ziarani, S. Bahar, A. Badiei, J Iran Chem Soc. 15 (2018) 1153.
40] S. Mahmoudi‐GomYek, D. Azarifar, M. Ghaemi, H. Keypour, M. Mahmoudabadi, Appl.
Organomet. Chem. 33 (2019) e4918.
[
[
41] M. Rajabi-Salek, M.A. Zolfigol, M. Zarei, Res. Chem. Intermed. 44 (2018) 5255.
42] I. Mel’nik, Y.L. Zub, B. Alonso, N. Abramov, P. Gorbik, C, Glass Phys. Chem. 38 (2012) 96.
[
Dear Editor
I didn’t see this letter before
I don’t know, how I can prepare it
Please help me if it is necessaire.
Sincerely yours
Dr. Mohammadi
Graphical abstract
1
5

R2
HO3S
SO3H
SO3H
HO3S
O
N
R1
O
O
HO3S
N
NH2
SO3H
CN
CN
N
N
N
SO3H
N
O
+
CN
O
SO3H
SO3H
Si
O
N
O
O
Si
O
O
HO3S
O
Si
O
O
Fe3O4
SiO2
O
O
O
SO H
O
3
O
Si
O
N
O O
O
Si
O
HO3S
N
Si
N
N
N
SO3H
SO3H
HO3S
N
HO3S
HO3S
Solvent-free, 60 °C
SO3H
Solvent-free, 60 °C
NC
O
CN
+
O
O
H N R1
2
R1
OEt
1
6

HO3S
SO3H
R2
SO3H
HO3S
O
O
HO3S
N
O
N
R1
CN
CN
SO3H
N
N
N
SO3H
N
+
NH2
SO3H
O
SO3H
Si
O O O
N
CN
O
Si
O
O
HO3S
O
Si
O
O
Fe3O4
SiO2
O
O
O
SO H
O
3
O
Si
O
N
O O
O
Si
O
HO3S
N
Si
N
N
N
SO3H
SO3H
HO3S
N
Solvent-free, 60 °C
HO3S
HO3S
Solvent-free, 60 °C
SO3H
NC
O
CN
+
R1
O
O
H N R1
2
OEt
1
7

HO3S
SO3H
SO3H
HO3S
HO3S
N
SO3H
N
N
N
SO3H
CN
CN
SO3H
O
O
SO3H
Si
O
N
+
O
N
O
R2
Si
O
O
O
HO3S
Si
O
O
Fe3O4
SiO2
O
O
N
R1
O
O
O
SO H
O
3
Si
O
NH2
N
O
O
O
O
Si
HO3S
N
Si
N
O
CN
O
N
N
SO3H
SO3H
N
HO3S
Solvent-free, 60 °C
Solvent-free, 60 °C
HO3S
HO3S
SO3H
NC
O
CN
H N
2
R1
+
O
O
R1
OEt
1
8

HO3S
SO3H
SO3H
HO3S
HO3S
N
SO3H
N
N
N
SO3H
CN
CN
SO3H
O
O
SO3H
Si
O
N
+
O
N
O
R2
Si
O
O
O
HO3S
Si
O
O
Fe3O4
SiO2
O
O
N
R1
O
O
O
SO H
O
3
Si
O
NH2
N
O
O
O
O
Si
HO3S
N
Si
N
O
CN
O
N
N
SO3H
SO3H
N
HO3S
Solvent-free, 60 °C
Solvent-free, 60 °C
HO3S
HO3S
SO3H
NC
O
CN
H N
2
R1
+
O
O
R1
OEt
1
9

HO3S
SO3H
SO3H
HO3S
HO3S
N
SO3H
N
N
N
SO3H
CN
CN
SO3H
O
O
SO3H
Si
O
N
+
O
N
O
R2
Si
O
O
O
HO3S
Si
O
O
Fe3O4
SiO2
O
O
N
R1
O
O
O
SO H
O
3
Si
O
NH2
N
O
O
O
O
Si
HO3S
N
Si
N
O
CN
O
N
N
SO3H
SO3H
N
HO3S
Solvent-free, 60 °C
Solvent-free, 60 °C
HO3S
HO3S
SO3H
NC
O
CN
H N
2
R1
+
O
O
R1
OEt
2
0

Author declaration
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Potential conflict of interest exists:
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[
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