Fe3O4@SiO2-copper sucrose xanthate as a green nanocatalyst for N-, O- and S-arylation

Article abstract of DOI:10.1002/aoc.4619

Formation of C(sp²)–X bonds was carried out using a Fe₃O₄@SiO₂-copper(I) sucrose xanthate nanoparticle catalyst with the aid of the copper(I) xanthate moiety in the catalyst which was prepared from the reaction between sucrose and carbon disulfide through an alkaline medium via the traditional Zeise approach. Various techniques were employed for the characterization of these novel nanoparticles. Three sorts of heteroatoms, N, O and S, successfully underwent heteroatom arylation to produce secondary or tertiary amines, ethers and thioethers, respectively.

Full text of DOI:10.1002/aoc.4619

Received: 7 June 2018
DOI: 10.1002/aoc.4619
Revised: 6 September 2018
Accepted: 7 September 2018
F U L L P A P E R
Fe3O4@SiO2‐copper sucrose xanthate as a green
nanocatalyst for N‐, O‐ and S‐arylation
Iman Radfar
| Maryam Kazemi Miraki
| Naghmeh Esfandiary
| Leila Ghandi
|
Akbar Heydari
Chemistry Department, Tarbiat Modares
University, PO Box 14155‐4838, Tehran,
Iran
Formation of C(sp2)–X bonds was carried out using a Fe3O4@SiO2‐copper(I)
sucrose xanthate nanoparticle catalyst with the aid of the copper(I) xanthate
moiety in the catalyst which was prepared from the reaction between sucrose
and carbon disulfide through an alkaline medium via the traditional Zeise
approach. Various techniques were employed for the characterization of these
novel nanoparticles. Three sorts of heteroatoms, N, O and S, successfully
underwent heteroatom arylation to produce secondary or tertiary amines,
ethers and thioethers, respectively.
Correspondence
Akbar Heydari, Chemistry Department,
Tarbiat Modares University, PO Box
14155‐4838, Tehran, Iran.
Email: heydar_a@modares.ac.ir
KEYWORDS
carbon–heteroatom coupling, copper, sucrose, Ullmann coupling, xanthate
1 | INTRODUCTION
sugars are considered less harmful and could be used as
individual promoters to interact with copper. For this
Incorporations of the three most common heteroatoms
(X: N, O and S) into organic frameworks specially in
C(sp2‐aromatic)–X bond systems has gained attention
owing to a wide variety of applications such as pharma-
ceutical, polymer and synthetic usages.[1] Ullmann
coupling has been introduced as the best way for produc-
tion of pharmaceutical and natural building blocks. Dur-
ing the last few decades, C–X cross‐coupling has been
developed using various transition metals such as Pd, Ni
or Cu as appealing catalysts, Cu being the most econom-
ically justifiable.[2] Copper‐based materials have attracted
considerable attention due to the stability of their varied
oxidation forms from 0 to +3 in various transformation
processes. As an outcome, this metal can be easily associ-
ated with some fields in organometallic chemistry.
During the past 20 years many endeavours have been
reported for the improvement of catalysts and media.[2–4]
Achieving a sustainable catalyst demands a recoverable
support like magnetic nanoparticles, the nanoscale bene-
fits of which have previously been revealed.[5] Design of a
stable core meets the demand of a strict shell between the
main linker and magnetic part. Among organic linkers,
purpose, various hydroxyl sites of a sugar can be altered
into dithiocarbonates through the Zeise method. The
dithiocarbonate group with respect to general yellowish
orange colour is also called a xanthate. The long history
of xanthates as sulfur analogues goes back two centuries.
One century later, Brandenberger synthesized a new
polyxanthate called cellophane of cellulose.[6] Continuing
such trends, firstly Mikhlin and co‐workers developed a
new strategy for producing copper xanthate in colloidal
phase and nanoscale size and demonstrated that copper
occurs as Cu(I).[7]
As a review of previous works, many procedures have
been developed for Ullmann coupling as the best way for
the production of pharmaceutical and of natural building
blocks. Among them, copper salts[8,9] for aryl ethers,
Pd@IL‐PMO,[10] copper(II) sulfate,[11] [Pd(C3H5)Cl]2/
ligand,[12] CuI/HBF4,[13] IMes‐Cu‐Cl,[14] NiCl2⋅6H2O,[15]
FeCl3⋅6H2O/L‐proline,[16] copper(II) acetate[17] and
FeCl2/CuO[18] for aryl thioethers are examples of
catalysts.
Herein, in continuation of our research on the prepa-
ration of new recoverable magnetic nanoparticles
Appl Organometal Chem. 2018;e4619.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4619

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RADFAR ET AL.
functionalized with sugars and their applications in
organic synthesis,[5] we report an efficient method for
synthesis of the novel Fe3O4@SiO2‐copper(I) sucrose xan-
thate (Fe3O4@SiO2‐CSX) and an investigation of its appli-
cation for carbon–heteroatom (N, O, S) cross‐coupling
reactions.
analyser with a heating rate of 20°C min−1 over the
temperature range 25–900°C under flowing compressed
nitrogen (as inert gas).
2.2 | Catalyst preparation
2.2.1 | Preparation of chlorinated
Fe3O4@SiO2 nanoparticles
2 | EXPERIMENTAL
2.1 | General
Experimentally, in a typical procedure, Fe3O4 nanoparti-
cles were prepared through a previously reported method
from iron(II) and iron(III) salts as sources in a strongly
basic medium (NH3 25% standard solution), with
dropwise addition of ammonia into an equimolar
solution of iron(II) and iron(III). Then the solution was
heated to 80°C for 6 h to complete the procedure of
formation and finally washing was done with distilled
water to achieve pure Fe3O4 in brown to black colour.[19]
The next step was carried out to form a silica shell using
tetraethyl orthosilicate (TEOS) in basic aqueous medium
with pH of around 11.[19] After neutralization of solution
and decanting using an external magnet, the shell was
chlorinated using thionyl chloride (SOCl2) in dried
CHCl3. Then, the resulting product was washed with
dry CHCl3 and dried under vacuum at 60°C for 2 h for
further reaction.
The solvents and starting materials were commercially
selected of synthesis grade and purchased from Merck
and Acros. Fourier transform infrared (FT‐IR) spectra
were collected with a Nicolet IR100 FT‐IR spectrometer
in the wavenumber range 400–4000 cm−1 using
spectroscopic‐grade KBr. The melting points of prod-
ucts were determined using a Barnstead Electronics
9100. The 1H NMR (500 MHz) spectra were recorded
using a Bruker Avance DPX‐500NMR spectrometer
with samples in CDCl3 as solvent. The morphology of
the catalyst was studied using scanning electron
microscopy (SEM; Philips XL 30 and S‐4160) with
coated gold equipped with energy‐dispersive X‐ray
(EDX) spectroscopy capability. Powder X‐ray diffraction
(XRD) patterns were recorded at room temperature
with a Philips X‐Pert 1710 diffractometer using Co Kα
radiation (λ = 1.78897 Å) at a voltage of 40 kV and
current of 40 mA to define the crystalline structure of
the catalyst nanoparticles. Data were collected from
10° to 90° (2θ) with a scan speed of 0.04° s−1. The
magnetic properties were measured with a vibrating
magnetometer/alternating gradient force magnetometer
(MD Co., Iran, www.mdk‐magnetic.com). Thermogravi-
metric analysis (TGA) was performed using a thermal
2.2.2 | Preparation of sodium sucrose
xanthate (SSX)
SSX was prepared using the Zeise method. An amount of
40 mmol of sodium hydroxide was added to a solution of
5 mmol of sucrose in 25 ml of hot water and stirred for
30 min at 80°C. Then, CS2 (40 mmol) was added dropwise
to the mixture and heated for 24 h at 80°C. The colour of
SCHEME 1 Catalyst preparation

RADFAR ET AL.
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the solution gradually became yellow and then towards
the completion of the reaction it changed to orange. The
product was then dried at 100°C for 3 h and the resulting
orange‐red solid had a sharp sulfur odour.
As can be seen in Figure 1, the major peaks appeared at
563 cm−1 (Fe─O stretching), 619 cm−1 (Cu─S stretching),
1050 cm−1 (Si─O stretching), 1345 cm−1 (Cu─S─C═O
stretching), 1412 cm−1 (Si─O stretching), 1571 cm−1
(dixanthogene) and 3413 cm−1 (hydroxyl O─H).
The crystal structure of Fe3O4@SiO2‐CSX was con-
firmed from its XRD pattern (Figure 2). The characteristic
peaks are compatible with the standard Fe3O4 (corre-
sponding to JCPDS 75‐0033 reference)[20] and the crystal
structure of pure Fe3O4 remains unchanged after immo-
bilization of Cu. The broad peak appearing at 21.46° is
attributed to Si.
The magnetism of Fe3O4@SiO2‐CSX nanoparticles
was analysed via VSM in the range −10 000 to
+10 000 Oe. From Figure 3, the saturation magnetization
is 10.4 emu g−1 and, as shown in Figure 3, the M(H)
hysteresis loop was completely reversible. Hence, these
results indicate that the nanoparticles have superpa-
ramagnetic behaviour.
2.2.3 | General procedure for preparation
of Fe3O4@SiO2‐CSX
Chlorinated Fe3O4@SiO2 (0.5 g) was added to a solution
of SSX (3 mmol, 3.378 g) in dried toluene (10 ml) and then
refluxed for 24 h. Afterwards, the greenish‐black solid was
magnetically separated and washed with water to remove
excess SSX and dried at room temperature under vacuum.
Subsequently, according to Mikhlin's instruction, in 8 ml
of acetonitrile–methanol (4/1 v/v), the synthesized SSX
(0.5 g) was reacted with 1 mmol of copper(II) acetate.
The mixture has heated for 4 h at 70°C and the resulting
greenish‐black solid (Fe3O4@SiO2‐CSX) was decanted
using an external magnet, washed two times with 5 ml
of deionized water and dried at room temperature under
vacuum.
The Figure 4a shows SEM images of Fe3O4@SiO2‐
CSX nanoparticles. According to the images, the surface
morphology of the nanoparticles is uniform. The average
size of the nanoparticles was estimated at around 50 nm
(spherical shape) with the least possible agglomeration
2.3 | General procedure for C–X cross‐
coupling
To a stirred solution of phenylboronic acid (1 mmol) and
aniline (N) or phenol/benzyl alcohol (O) or thiophenol(S)
(1 mmol) in CH2Cl2 (3 ml) was added 50 mg of catalyst
and refluxed (at 40°C) for 20 h. Then, the catalyst was
separated using an external magnet and the pure product
was obtained with a non‐flash silica gel column.
3 | RESULTS AND DISCUSSION
The characterization of the catalyst was performed using
several techniques: FT‐IR spectroscopy, XRD, vibrating
sample magnetometry (VSM), SEM–EDX, TGA and
inductively coupled plasma (ICP) analysis. Scheme 1
illustrates the synthetic method of Fe3O4@SiO2‐CSX.
FIGURE 2 XRD pattern for Fe3O4@SiO2‐CSX nanoparticles
FIGURE 1 FT‐IR spectrum of CSX nanoparticles
FIGURE 3 VSM diagram of Fe3O4@SiO2‐CSX nanoparticles

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RADFAR ET AL.
FIGURE 4 (a) SEM images and (b) EDX analysis of Fe3O4@SiO2‐CSX nanoparticles
as shown in 500 nm scaled SEM image (Figure 4a). Also,
the presence of sulfur and copper as an evidence for suc-
cessful immobilization of SSX and Cu(II) cation onto the
primary Fe3O4@SiO2 was confirmed via EDX analysis
(Figure 4b).
The next measurement was that of the amount of
organic material grafted on the primary Fe3O4@SiO2.
TGA revealed that about 24.74% (w/w) of catalyst mass
is lost between 100 and 650°C and this result is indicative
of the mass percentage of organic motif joined to the

RADFAR ET AL.
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FIGURE 5 TGA/DTG/DTA curves of
Fe3O4@SiO2‐CSX nanoparticles
surface of catalyst nanoparticles. Such decrease in mass is
completely a result of degradation of sugar and linked
CS2 as organic motifs in the nanoparticles (Figure 5).
To provide validated evidence of the remaining cop-
per in the synthesis step and after four catalytic runs,
ICP analysis was performed. ICP measurements revealed
that there are 0.345 and 0.170 mmol of copper per gram
of catalyst before and after four repeat reactions, respec-
tively. These results showed that the amount of copper
linked on the nanoparticles has noticeably decreased
and around half of the initial copper was released after
the reaction; however, it is worth noting that the synthe-
sized catalyst is still reliable comparing with other hetero-
geneous copper‐based catalysts. It is worthwhile to
mention the role of copper as catalyst in C–X coupling
through oxidative addition and reductive elimination.
Only the nanoparticles from the last step of interaction
of copper with xanthate can play the role of desired cata-
lyst, and not those of earlier steps of the preparation with-
out copper.
The coupling reactions did not occur in the absence of
the catalyst and base, so catalyst and base played an
important role in the transformation (Table 1). When
we used Fe3O4@SiO2‐CSX as catalyst and K2CO3 as base,
the desired products were obtained in moderate yields.
When other bases such as pyridine, Et3N, DBU, DBN,
Na2CO3, NaHCO3, NaOH and KOH were used, the best
yield was ultimately afforded by Et3N. Among the sol-
vents, the use of refluxing CH2Cl2 as solvent offered the
best results. With regard to the amount of catalyst, using
50 mg of Fe3O4@SiO2‐CSX was sufficient and using a
greater amount was ineffective. Surprisingly, when using
aryl halides (phenyl bromide and phenyl iodide) instead
of phenylboronic acid, the yield of the reaction decreased
obviously. Such a decrease is theoretically because of the
initial insertion pace that naturally has a competition
between C─B and C─X (X: Br or I) bonds. The highest
yields for Et3N as base proved the preferable aspect of
the present technique because of its easily volatile nature
meaning it can smoothly be removed at temperatures
lower than boiling points of liquid products.
Initially, to evaluate the catalytic efficiency of
Fe3O4@SiO2‐CSX, C–X cross‐coupling reactions between
aniline/phenol/thiophenol and phenylboronic acid were
chosen as model reactions (Scheme 2) and the influences
of solvent, amount of catalyst, base, temperature and
reaction time were investigated to develop optimized
conditions.
From a literature survey, some results for previously
reported similar C–X couplings are presented in Table 2.
Under the optimized conditions, the C–X cross‐
coupling of arylamines, phenols (benzyl alcohol) and
thiophenols was investigated. The reaction proceeded
with both electron‐donating and electron‐withdrawing
nucleophiles for obtaining the corresponding amines,
ethers and thioethers. Scheme
3 shows that the
N‐arylation reaction proceeded smoothly from anilines
containing different electron‐donating groups (2a). How-
ever, target products could not be synthesized in consid-
erable yield for electron‐deficient aromatic systems (9a).
This protocol efficiently coupled aliphatic amines with
phenylboronic acid to provide the desired products in
SCHEME 2 Model reactions for C–X cross‐coupling

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RADFAR ET AL.
TABLE 1 Optimizing reaction conditions in the C–X cross‐coupling catalysed by Fe3O4@SiO2‐CSX
Entry
Base
Catalyst (mg)
Solvent (3 cm3)
Temp. (°C)
Time (h)
Yield (%) 2.5%
1
—
—
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
30
50
75
50
—
50
CH2Cl2
1,4‐Dioxane
1,4‐Dioxane
CH2Cl2
CH3CN
THF
40
70
70
40
82
66
77
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
20
20
20
20
20
20
20
20
30
40
10
20
20
20
20
20
20
20
20
20
20
20
20
20
20
0, 0, 0a
2
Et3N
70, 60, 75
55, 50, 65
45, 30, 40
45, 20, 40
65, 40, 55
40, trace, 40
80, 65, 85
75, 65, 85
75, 65, 85
70, 55, 70
65, 40, 50
40, 60, 70
40, 50, 70
30, 20, 40
45, trace, 30
35, 20, 40
65, 45, 65
70, 55, 65
60, 37, 70
80, 70, 90
80, 70, 90
trace, 0, 0
0, 0, 0
3
K2CO3
K2CO3
Et3N
4
5
6
Et3N
7
Et3N
EtOAc
8
Et3N
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
Solvent‐free
9
Et3N
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Et3N
Et3N
Pyridine
KOH
NaOH
Na2CO3
NaHCO3
K3PO4
DBU
DBN
Et3N
Et3N
Et3N
—
Et3N
Et3N
15, 0, 20
aYield: C─N (Ph2NH), C─O ((Ph‐CH2)─O─Ph), C─S (Ph─S─(C6H4─Me)).
TABLE 2 Survey of some of previously reported C–X couplings
Entry
Substrate
Catalyst
Base
Solvent/temp.
DME/80°C
Yield (%)
1
Ph‐I/imidazolePh‐I/Ph‐OH
Ph‐I/Ph‐SH
CuI/N,N′‐dioxide ligands
Note: homogeneous catalyst
Cs2CO3
95[2]
98
95
[21]
2
p‐Tol‐B(OH)2/4‐NH2‐Pyridine
p‐Tol‐B(OH)2/2‐NH2‐Pyridine
Cu (OAc)2
Pyridine
CH2Cl2/r.t.
74
23
[22]
3
4
Cyclohexyl‐SH/Ph‐B(OH)2
Cu(OAc)2/4 Å MS
Pyridine
K2CO3
—
88
[10]
Ph‐Br/Ph‐SH
Ph‐I/Ph‐SH
Pd@IL‐PMO
H2O/100°C
88
96
[11]
5
6
7
8
9
Ph‐B(OH)2/Ph‐SH
Ph‐I/Ph‐SH
CuSO4/10‐Phen.H2O
IMes‐Cu‐Cl
n‐Bu4N─OH
LiOBut
KOH
EtOH/r.t.
83
[14]
Toluene/120°C
TBAB
82
[15]
Ph‐I/Ph‐SH
NiCl2.6H2O
99
[16]
4‐Ac‐C6H4‐I/Ph‐SH
FeCl3.6H2O/L‐Proline
FeCl2⋅4H2O/CuO
KOH
TBAB/H2O/130°C
DMF/135°C
95
[18]
6‐Iodoimidazo[1,2‐a]pyridine/Ph‐SH
6‐Iodoimidazo[1,2‐a]pyridine/imidazole
Cs2CO3
60
50

RADFAR ET AL.
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SCHEME 3 Scope of the three types of C–X cross‐coupling reactions
good yields. Under the optimized conditions, sulfonamide
was reacted with phenylboronic acid to produce the
desired product. Also, having identified the optimal
conditions, the scope and versatility of this method was
extended to the reaction of various phenols with
phenylboronic acid Generally, phenols having electron‐
withdrawing groups gave the related product in excellent
yields in comparison to electron‐donating ones. Although
4‐nitrophenol gave high yield of cross‐coupled products,
the more sterically hindered 2,4,6‐trinitrophenol
(picric acid) generated only in moderate amounts the
The proposed mechanism for the coupling reactions is
depicted in Scheme 4. The oxidative addition of aryl
halide to Fe3O4@SiO2‐CSX occurs to give Cu intermedi-
ate A. Then, deprotonation of amine/phenol/thiophenol
and ligand exchange produce Cu intermediate B. Finally,
the desired cross‐coupled product is easily provided by
reductive elimination.
O‐arylation
produced target products in good yield. Notably,
N‐hydroxyphthalimide could be reacted with
product.
However,
benzyl
alcohol
phenylboronic acid to afford the desired product in moder-
ate yield. Moreover, we investigated the catalytic efficiency
of Fe3O4@SiO2‐CSX for coupling of phenylboronic acid
and various iodobenzene derivatives with thiols. Excellent
conversion was obtained for these reactions between
various thiols and phenylboronic acid (1c–3c) and
iodobenzene derivatives having both electron‐donating
and electron‐withdrawing groups (4c–6c). It should be
noted that there was no coupling between currently used
nucleophiles and aryl chlorides.
SCHEME 4 Possible suggested mechanism of C–X coupling

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RADFAR ET AL.
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How to cite this article: Radfar I, Kazemi Miraki
M, Esfandiary N, Ghandi L, Heydari A.
Fe3O4@SiO2‐copper sucrose xanthate as a green
nanocatalyst for N‐, O‐ and S‐arylation. Appl
Organometal Chem. 2018;e4619. https://doi.org/
10.1002/aoc.4619
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457.
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.