A green and efficient Pd-free protocol for the Suzuki–Miyaura cross-coupling reaction using Fe3O4@APTMS@Cp2ZrClx(x = 0, 1, 2) MNPs in PEG-400

Article abstract of DOI:10.1007/s11164-020-04145-4

Abstract: In this paper, a new application of the Fe₃O₄@APTMS@Cp₂ZrCl_{x(x = 0, 1, 2)} MNPs as a robust and highly efficient Pd-free catalytic system in the environmentally benign Suzuki–Miyaura cross-coupling reaction has been demonstrated. The use of the recyclable Pd-free catalyst and PEG-400 as a green solvent, relatively short and acceptable reaction times, and good-to-excellent yields of the pure bi-aryl products are some of the salient features of the current carbon–carbon cross-coupling synthetic strategy. Graphic abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s11164-020-04145-4

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-020-04145-4
A green and efcient Pd‑ꢀree protocol
ꢀ
or the Suzuki–Miyaura cross‑coupling reaction using
Fe O @APTMS@Cp ZrCl MNPs in PEG‑400
3
4
2
x(x = 0, 1, 2)
Behzad Zeynizadeh · Hossein Mousavi1 · Farhad Sepehraddin1
1
Received: 5 December 2019 / Accepted: 30 March 2020
©
Springer Nature B.V. 2020
Abstract
In this paper, a new application of the Fe O @APTMS@Cp ZrCl MNPs
3
4
2
x(x = 0, 1, 2)
as a robust and highly eꢀcient Pd-free catalytic system in the environmentally
benign Suzuki–Miyaura cross-coupling reaction has been demonstrated. The use of
the recyclable Pd-free catalyst and PEG-400 as a green solvent, relatively short and
acceptable reaction times, and good-to-excellent yields of the pure bi-aryl products
are some of the salient features of the current carbon–carbon cross-coupling syn-
thetic strategy.
Graphic abstract
Keywords Cross-coupling reaction · Suzuki–Miyaura reaction · Green chemistry ·
Magnetically nanocatalyst · Zirconium-containing catalyst · PEG-400
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4
-020-04145-4) contains supplementary material, which is available to authorized users.
*
Hossein Mousavi
hossein.mousavi@gmail.com
1
1
Department of Organic Chemistry, Faculty of Chemistry, Urmia University, Urmia, Iran
Vol.:(012
1
3456789)
3

B. Zeynizadeh et al.
Introduction
The formation of Caryl–C bonds to achieve a variety of valuable bi-aryl compounds
aryl
is of great value in synthetic chemistry [1–10]. In this regard, the Suzuki–Miyaura
cross-coupling reaction is one of the well-known, convenient, highly eꢀcient, and reli-
able synthetic strategies for the generation of diverse bi-aryl species. In recent years,
the Suzuki–Miyaura cross-coupling reaction was used extensively in the synthesis of
polymers, agrochemicals, alkaloids, pharmaceutical intermediates, biologically active
compounds, pigments (or dyes), OLED emitters, liquid crystals, chemosensors, and so
on (Fig. 1) [11–55].
Scrutinizing published papers in the area of the Suzuki–Miyaura reaction clearly
shows that most of the existing protocols are based on palladium (Pd), and very few
Pd-free methods have been reported. Therefore, the development of the new Pd-free
catalytic systems for the Suzuki–Miyaura cross-coupling reaction is precious. Besides,
the importance and unique properties of the earth-abundant transition metal (EATM)-
based magnetic and non-magnetic nanoparticles [56] have made the use of such cata-
lytic systems to take priority for the Pd-free Suzuki–Miyaura C –C cross-coupling
aryl
aryl
reaction.
One of the inꢁuential factors in green chemistry is catalysis [57–71]. Although
magnetically catalytic systems have a special place in green organic synthesis [72–97],
regrettably, the presence of metal in their structure (especially in the shell part of the
core–shell type of magnetically nanocatalysts) is always a concern from an environ-
mental standpoint. In 2019, Bystrzanowska, Petkov, and Tobiszewski ranked some
heterogeneous metal catalysts in the order of greenness using a multicriteria decision
analysis (MCDA) approach [98]. Their investigation and ranking table (based on met-
als) demonstrated Zr-containing heterogeneous catalytic systems are environmentally
desirable than Rh-, Cu-, Cd-, Pd-, Au-, Co-, and also Ni-based systems.
On the other hand, one of the signiꢂcant aspects not only in the Suzuki–Miyaura
reaction but also in all types of chemical reactions is solvent in the green chemistry
point of view [99–106]. One of the excellent choices as a green solvent in organic
synthesis is polyethylene glycol (PEG), due to its attractive features like non-toxicity,
inexpensive, thermally stable, polar nature, biocompatibility, biodegradability, and also
recyclability [107–110].
In continuation of our research program [111–117] and also due to the high impor-
tance of developing green and eꢀcient Pd-free protocols for the Suzuki–Miyaura cross-
coupling reaction, herein we wish to report a novel, environmentally benign, and con-
venient Pd- and phosphine-free strategy for the mentioned reaction using magnetically
separable Fe O @APTMS@Cp ZrCl NPs in PEG-400 (Scheme 1).
x(x = 0, 1, 2)
3
4
2
Results and discussion
First of all, we prepared the Fe O @APTMS@Cp ZrCl MNPs accord-
x(x = 0, 1, 2)
3
4
2
ing to our previous report (Scheme 2) [117]. Also, the structure of the as-pre-
pared core–shell-type catalytic system was identiꢂed by Fourier transform
1
3

A green and efcient Pd‑ꢀree protocol ꢀor the Suzuki–Miyaura…
Fig. 1 Some examples of the Suzuki–Miyaura cross-coupling reaction (see dark pink bonds) applications
in the synthesis of useful materials
infrared (FT-IR) spectroscopy, X-ray diꢃraction (XRD), scanning electron micros-
copy (SEM), energy-dispersive X-ray spectroscopy (EDX), inductively coupled
plasma-optical emission spectrometry (ICP-OES), alternative gradient ꢂeld mag-
netometer (AGFM), thermogravimetric analysis (TGA), and also N adsorp-
2
tion–desorption analysis.
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3

B. Zeynizadeh et al.
Scheme 1 The Suzuki–Miyaura cross-coupling reaction in the presence of Fe O @APTMS@
3
4
Cp ZrCl
as a Pd-free nanocatalyst in PEG-400
2
x(x = 0, 1, 2)
Scheme 2 Preparation steps of the Fe O @APTMS@Cp ZrCl MNPs
x(x = 0, 1, 2)
3
4
2
1
3

A green and efcient Pd‑ꢀree protocol ꢀor the Suzuki–Miyaura…
The FT-IR spectra of the prepared Fe O , Fe O @APTMS, and Fe O @
3
4
3
4
3
4
APTMS@Cp ZrCl
nanomaterials are presented in Fig. 2. The FT-IR spec-
2
x(x = 0, 1, 2)
trum of the unmodiꢂed Fe O NPs (blue curve) displayed an intense absorption
3
4
−1
peak at 588 cm for the stretching of the Fe–O bond along with a broadband at
−1
around 3370 cm , which denoted to the stretching vibration of the surface –OH
groups. Also, as shown in Fig. 1, bending vibrations of the mentioned surface
−1
−1
–
OH groups appeared at 1621 cm and 1401 cm . In the FT-IR spectrum of the
−
1
Fe O @APTMS NPs (Fig. 2, orange curve), appearance signals at 1621 cm and
3
4
−1
1
272 cm are assigned to the bending vibrations of the –OH and –NH groups.
2
−1
Notably, the characteristic broad peak at 3442 cm belongs to the stretching vibra-
tions of the mentioned –OH and –NH groups, of the Fe O @APTMS NPs. Further-
2
3
4
−1
more, the absorption band at 1040 cm that corresponding to the stretching vibra-
−
1
tion of the Si–O groups, along with the peaks at 2933–2850 cm , that depending on
the stretching vibration of the CH groups, conꢂrmed that the surface of the Fe O
4
2
3
NPs successfully is modiꢂed by APTMS. Finally, the existence of all the mentioned
former peaks in the FT-IR spectrum of the Fe O @APTMS@Cp ZrCl
x(x = 0, 1, 2)
3
4
2
−
1
(
light gray curve) along with a new sharp peak at 1616 cm , which belongs to the
C=C of the cyclopentadienyl (Cp) moieties, is evidence for the construction of the
as-prepared zirconocene-containing catalytic system.
As shown in Fig. 3, in the XRD pattern of the Fe O @APTMS@Cp Zr-
3
4
2
Cl
MNPs, the characteristic peaks of the Fe O have existed after two
x (x = 0, 1, 2)
3 4
modiꢂcation steps by APTMS and Cp ZrCl . Notably, the mentioned peaks at
2
2
(
111), (220), (311), (400), (422), (511), (440), (620), and also (553) are attributed
to the cubic spinel phase of the Fe O which matched well with the literature
3
4
data from the Joint Committee on Powder Diꢃraction Standards (JCPDS, ꢂle nos.
Fig. 2 FT-IR spectra of the prepared Fe O , Fe O @APTMS, and Fe O @APTMS@Cp ZrCl
3
4
3
4
3
4
2
x(x = 0, 1, 2)
nanomaterials
1
3

B. Zeynizadeh et al.
7
9-0418, 65-3107, 74-2402, and also 98-007-7842). It is worth noting the distinc-
tive peaks of the pure zirconium [118] overlapped with the Fe O peaks in the
3
4
XRD pattern.
To visualize the morphology and particle dimension of the Fe O @APTMS@
3
4
Cp ZrCl
MNPs, the SEM images of the as-prepared nanocatalyst were
2
x(x = 0, 1, 2)
recorded with various magniꢂcations. The SEM images disclosed that the zir-
conocene-containing magnetically nanocatalyst has a nearly spherical morphol-
ogy with diameters less than 15 nm (Fig. 4).
The chemical identiꢂcation of the Fe O @APTMS@Cp ZrCl MNPs
x(x = 0, 1, 2)
3
4
2
contained elements determined by the EDX spectroscopy technique (Fig. 5). The
resulting EDX spectrum demonstrated the presence of all the expected compo-
nents (viz. Fe, O, C, Zr, Si, N, and Cl) in the structure of the as-prepared nano-
catalyst. The presence of the Zr and Cl peaks in the EDX spectrum conꢂrmed the
deposition of the zirconocene dichloride (Cp ZrCl ) on the surface of the Fe O @
2
2
3
4
APTMS MNPs successfully done. Moreover, by the ICP-OES, the exact amount
of Fe and Zr in the structure of the Fe O @APTMS@Cp ZrCl MNPs
3
4
2
x(x = 0, 1, 2)
was calculated as 52.75% and 3.72%, respectively.
Having an acceptable magnetic property for a magnetic catalyst system is one
of the signiꢂcant factors which has a great eꢃect on the separation of the cata-
lyst from the reaction medium and prevents contamination in the product or envi-
ronment. In this regard, magnetic properties of the prepared Fe O and Fe O @
3
4
3
4
APTMS@Cp ZrCl
NPs are illustrated by AGFM data at room tempera-
2
x(x = 0, 1, 2)
ture (Fig. 6). The AGFM curves indicated that the bare Fe O NPs and Fe O @
3
4
3
4
Fig. 3 XRD pattern of the as-prepared Fe O @APTMS@Cp ZrCl MNPs
x(x = 0, 1, 2)
3
4
2
1
3

A green and efcient Pd‑ꢀree protocol ꢀor the Suzuki–Miyaura…
Fig. 4 SEM images of the prepared a, b Fe O and c–f Fe O @APTMS@Cp ZrCl nanomateri-
x(x = 0, 1, 2)
3
4
3
4
2
als
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B. Zeynizadeh et al.
Fig. 5 EDX spectrum of the as-prepared Fe O @APTMS@Cp ZrCl MNPs
x(x = 0, 1, 2)
3
4
2
APTMS@Cp ZrCl
NPs have saturation magnetizations (Ms) values as
x(x = 0, 1, 2)
2
0
.13 a.u., and 0.095 a.u., respectively. The mentioned AGFM information not
only proved that the modiꢂcation processes have been completed and also showed
that the as-prepared core–shell magnetically nanocatalyst can be easily and
quickly removed from the reaction environment using an external magnetic ꢂeld.
Fig. 6 AGFM curves of a Fe O and b Fe O @APTMS@Cp ZrCl magnetically nanomaterials
x(x = 0, 1, 2)
3
4
3
4
2
1
3

A green and efcient Pd‑ꢀree protocol ꢀor the Suzuki–Miyaura…
The decomposition temperature of the as-prepared Fe O @APTMS@
3
4
Cp ZrCl
MNPs was investigated by TGA (Fig. 7). The weight loss hap-
2
x(x = 0, 1, 2)
pened under 200 °C owing to the removal of the surface –OH groups, adsorbed
solvent, and also moisture. Another weight loss occurred at 200–800 °C assigned
to the decomposition of the organic moieties, namely APTMS and zirconocene
groups. It should be noted that the striking diꢃerence between TGA curves of the
Fe O @APTMS (red curve) and Fe O @APTMS@Cp ZrCl (blue curve)
x(x = 0, 1, 2)
3
4
3
4
2
at 200–800 °C proved the presence of the zirconocene moiety in the ꢂnal structure
of the as-prepared magnetic nanocatalyst.
The nitrogen adsorption–desorption isotherms of the prepared Fe O and
3
4
Fe O @APTMS@Cp ZrCl nanomaterials are shown in Fig. 8. Based on
3
4
2
x(x = 0, 1, 2)
the IUPAC classiꢂcation, isotherms of the mentioned prepared materials are typical
type IV with an H1-type hysteresis loop. These results prove that the prepared nano-
materials have a mesoporous structure. Also, the speciꢂc surface area (S ) and
BET
total pore volume (V ) of the Fe O @APTMS@Cp ZrCl MNPs are also
total
3
4
2
x(x = 0, 1, 2)
2
−1
3
−1
found to be 81.31 (m g ) and 0.26 (cm g ), respectively.
After providing characterization of the zirconocene-containing magneti-
cally nanocatalyst, we tried to ꢂnd the optimal conditions for the new Pd-free
Suzuki–Miyaura cross-coupling reaction. In this regard, we initiated our stud-
ies from a model cross-coupling reaction of PhI (iodobenzene) and PhB(OH)
2
(
(
phenylboronic acid) to the synthesis of the most simplistic bi-aryl compound
viz. 1,1′-biphenyl) in the presence of 5 mg of the as-prepared Fe O @APTMS@
3
4
Cp ZrCl
nanocatalyst and 1.5 mmol of K CO (potassium carbonate) as
2
x(x = 0, 1, 2)
2 3
an inexpensive and readily available inorganic base in water at 70 °C (Table 1, entry
1
). Unfortunately, in this mode, the reaction time and yield of the desired product
were unsatisfactory. Also, the results of the experiments in EtOH (ethanol), EtOAc
ethyl acetate), and CH Cl (dichloromethane) were not satisꢂed (Table 1, entries
(
2
2
Fig. 7 TGA curves of the prepared Fe O , Fe O @APTMS, and Fe O @APTMS@Cp ZrCl
3
4
3
4
3
4
2
x(x = 0, 1, 2)
nanomaterials
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B. Zeynizadeh et al.
Fig. 8 N adsorption–desorption isotherms of the Fe O and Fe O @APTMS@Cp ZrCl nano-
x(x = 0, 1, 2)
2
3
4
3
4
2
materials
Table 1 Optimization of the reaction conditions
HO
Fe
3 4 2
O @APTMS@Cp ZrClx (x = 0, 1, 2)
I
+
B
Solvent, Base, Temperature, Time
HO
Entrya
Catalyst (mg)
Solvent
Base
Temperature Time (min)
°C)
Yield (%)
(
1
2
3
4
5
6
7
8
9
5
5
5
5
5
5
5
5
3
7
5
5
5
–
H O
K CO
70
70
70
60
60
70
70
25
70
70
70
70
70
70
180
90
120
140
120
25
20
230
60
20
35
120
180
180
71
75
76
69
71
96
98
87
85
98
60
64
58
N.R.
2
2
3
3
3
3
3
3
3
3
3
3
EtOH
EtOH
EtOAc
CH Cl
K CO
2
K CO
2
K CO
2
K CO
2
2
2
DMF
K CO
2
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
K CO
2
K CO
2
K CO
2
10
11
12
13
14
K CO
2
KOH
Et N
3
Pr N
3
K CO
2
3
a
PhI (1 mmol), PhB(OH) (1 mmol), solvent (2 mL), and base (1.5 mmol)
2
1
3

A green and efcient Pd‑ꢀree protocol ꢀor the Suzuki–Miyaura…
2
–5). Notably, DMF (N,N-dimethylformamide) was better than the mentioned sol-
vents in terms of both speed and eꢀciency (Table 1, entry 6). Surprisingly, when the
reaction was carried out in PEG-400 as a green solvent, the satisfying results were
obtained even better than when we used DMF (Table 1, entry 7). After ꢂnding the
suitable solvent, we repeated the reaction at room temperature (25 °C) and found
that in this mode, the reaction time is much longer, and the yield is reduced (Table 1,
entry 8). Also, we checked the eꢃect of the amount of the catalyst on the reaction.
When we reduced the amount of the catalyst from 5 to 3 mg, we found that the reac-
tion time was prolonged, and the yield of the desired product was reduced (Table 1,
entry 9). Interestingly, by increasing the amount of the catalyst from 5 to 7 mg, no
change was observed in the reaction process (Table 1, entry 10). Furthermore, we
investigated the eꢃect of the other bases, including KOH (potassium hydroxide),
Et N (triethylamine), and Pr N (tripropylamine) instead of K CO (Table 1, entry
3
3
2
3
1
1–13), and it was found that K CO is the most suitable base for this cross-coupling
2 3
reaction. Also, as it is quite clear, this reaction is not carried out in the catalyst-free
condition (Table 1, entry 14).
After optimization reaction conditions, the scope of the present Pd-free
Suzuki–Miyaura cross-coupling reaction was examined using the reaction between
various aryl(naphthyl) halides and phenylboronic acid. Although the correspond-
ing bi-aryl products obtained good-to-excellent yields, the reaction rate was strongly
inꢁuenced by the electron-donating and electron-withdrawing groups. In this con-
text, we observed that aryl halides containing electron-withdrawing substituents had
a higher rate rather than others. Furthermore, the turnover number (TON) and turno-
ver frequency (TOF) values for the mentioned Suzuki–Miyaura cross-coupling reac-
tion were calculated and are listed in Table 2.
It ought to note that the exact reaction mechanism of the Suzuki–Miyaura cross-
coupling reaction in the presence of the Fe O @APTMS@Cp ZrCl MNPs
x(x = 0, 1, 2)
3
4
2
is not explicit precisely. But, a plausible mechanism for the mentioned Pd-free
C
–C cross-coupling reaction is depicted in Scheme 3.
aryl
aryl
The recoverability and reusability of a catalyst are of prominent issues in terms
of cost-eꢃectiveness and environmental perspective. In this regard, after com-
pleting the current C –C cross-coupling reaction, the Fe O @APTMS@
aryl
aryl
3
4
Cp ZrCl
MNPs were collected from the reaction medium using an external
2
x(x = 0, 1, 2)
magnet and washed with EtOAc. Then, the reusability of the recovered nanocata-
lyst was examined using the Suzuki–Miyaura cross-coupling reaction of PhI with
PhB(OH) under optimal reaction conditions. As shown in Fig. 9, the as-prepared
2
magnetically nanocatalyst can be reused at least ꢂve runs without signiꢂcant loss in
catalytic activity.
It is worthwhile to note that in comparison with previously reported protocols
for the Pd-free Suzuki–Miyaura cross-coupling reaction, our method is green, cost-
eꢃective, and eꢀcient rather than most of them (Table 3). Furthermore, our pre-
sented strategy is signiꢂcantly faster than all of them.
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B. Zeynizadeh et al.
Table 2 Substrate scope for the Pd-free Suzuki–Miyaura cross-coupling reaction using Fe O @
3
4
APTMS@Cp ZrCl
MNPs
2
x(x = 0, 1, 2)
Time Yield
TON
TOF
(h )
Entry
R—X
Product
-
1
(
min)
(%)
1
20
98
480.641902 1441.925706
470.832884 627.777178
407.074264 444.081015
465.928375 1397.785125
392.360736 336.309203
407.074264 542.765685
475.737393 1902.949572
2
3
4
5
6
7
45
55
20
70
45
15
96
83
95
80
83
97
1
3

A green and efcient Pd‑ꢀree protocol ꢀor the Suzuki–Miyaura…
Table 2 (continued)
8
9
10
90
40
40
45
98
78
89
88
85
480.641902 2883.851412
382.551718 255.034479
436.501319 654.751979
431.596810 647.395215
416.883282 555.844377
1
1
1
0
1
2
TON (turnover number)=[(mmol of product formed)/(mmol of catalyst used)]
TOF (turnover frequency)=[TON/time (h)]
The TON and TOF values were calculated based on the existed amount of Zr in the nanocatalyst (in 5 mg
of the nanocatalyst, 0.186 mg (or 0.00203894 mmol) of Zr has existed)
Experimental
Reagents, samples, and apparatus
All reagents and solvents were purchased from commercial suppliers and
1
used without further puriꢂcation. H NMR spectra were recorded on a Bruker
Avance-300 DRX NMR Spectrometer at 300 MHz. FT-IR spectra were recorded
on a Nexus 670 Thermo Nicolet Fourier transform infrared (FT-IR) spectrometer
and measured as KBr discs. The crystalline structure of the as-prepared Fe O @
3
4
APTMS@Cp ZrCl
MNPs was surveyed by XRD on a Philips PANa-
2
x(x = 0, 1, 2)
lytical X’Pert Pro diꢃractometer (Netherlands). The size and morphology of the
1
3

B. Zeynizadeh et al.
Scheme 3 Proposed mechanism for the Suzuki–Miyaura cross-coupling reaction catalyzed by Fe O @
3
4
APTMS@Cp ZrCl
MNPs
2
x(x = 0, 1, 2)
Fe O and Fe O @APTMS@Cp ZrCl MNPs were investigated by SEM
x(x = 0, 1, 2)
3
4
3
4
2
images with FE-SEM TESCAN MIRA3. The chemical contents (especially Fe
and Zr) of the Fe O @APTMS@Cp ZrCl MNPs were detected by an
3
4
2
x(x = 0, 1, 2)
ICP-OES. The magnetic properties of the prepared Fe O and Fe O @APTMS@
3
4
3
4
1
3

A green and efcient Pd‑ꢀree protocol ꢀor the Suzuki–Miyaura…
9
8
9
5
95
95
94
100
8
6
4
2
0
0
0
0
0
23
20
20
21
21
Run 1
Run 2
Run 3
Run 4
Run 5
Time (min)
Yield (%)
Fig. 9 Recycling experiments of the Fe O @APTMS@Cp ZrCl
MNPs on the Suzuki–Miyaura
3
4
2
x(x = 0, 1, 2)
cross-coupling reaction
Cp ZrCl
NPs were measured by AGFM at room temperature. The TG
x(x = 0, 1, 2)
2
analyses were carried out using a Shimadzu DTG-60 instrument under a nitrogen
atmosphere. The N adsorption–desorption isotherms were measured by a BEL-
2
SORP-Max (BEL Japan, Inc.). Mass spectra were recorded on Agilent-5975C
inert XL MSD operating at ionization potential of 70 eV. Melting points were
determined on an Electrothermal 9200 apparatus.
Preparation of the Fe O @APTMS@Cp ZrCl MNPs
x(x = 0, 1, 2)
3
4
2
First, the reaction between 1.5 g of the Fe O NPs, which were prepared by the co-
3
4
precipitation protocol with 2 g of (3-aminopropyl)trimethoxysilane (APTMS) in
n-hexane as an organic solvent under reꢁux condition and N atmosphere, aꢃorded
2
Fe O @APTMS MNPs after 24 h. Next, 1 g of the prepared Fe O @APTMS MNPs
3
4
3
4
was dispersed in EtOH under ultrasonic irradiation for 10 min. After the mentioned
time, 1 g of zirconocene dichloride (Cp ZrCl ) was added into the reaction environ-
2
2
ment, and the resulting mixture was stirred for 10 h at reꢁux. Afterward, the mix-
ture was cooled to room temperature, and then the as-prepared Fe O @APTMS@
3
4
Cp ZrCl
MNPs were collected by an external magnet, washed with acetone
2
x(x = 0, 1, 2)
and then deionized (DI) water, and ꢂnally dried under vacuum for 6 h.
1
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B. Zeynizadeh et al.
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3

A green and efcient Pd‑ꢀree protocol ꢀor the Suzuki–Miyaura…
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B. Zeynizadeh et al.
General procedure for the presented Pd‑free Suzuki–Miyaura cross‑coupling
reaction
In a round-bottom ꢁask (15 mL) equipped with a magnetic stirrer, a mixture of
aryl(naphthyl) halide (1 mmol), phenylboronic acid (1 mmol), K CO (1.5 mmol),
2
3
and 5 mg of the Fe O @APTMS@Cp ZrCl MNPs in PEG-400 (2 mL) as
3
4
2
x(x = 0, 1, 2)
a green solvent was stirred at 70 °C in an oil bath. After completion of the C –C
aryl
aryl
cross-coupling reaction, the zirconocene-modiꢂed nanocatalyst was separated from
the reaction environment by an external magnet. Next, distilled water (5 mL) was
added, and the mixture was stirred for an additional 5 min. The bi-aryl product was
extracted with EtOAc (3×5 mL), and the organic layer was then dried over anhy-
drous Na SO . Finally, evaporation of the solvent under reduced pressure aꢃords the
2
4
crude bi-aryl compound following with a further puriꢂcation by short column chro-
matography on silica gel.
Conclusion
In summary, we have introduced a new, environmentally benign, and highly eꢀcient
Pd- and phosphine-free strategy for the Suzuki–Miyaura cross-coupling reaction
using robust magnetically reusable Fe O @APTMS@Cp ZrCl nanopar-
x(x = 0, 1, 2)
3
4
2
ticles in PEG-400. It should be noted that the presented Pd-free C –C cross-
aryl
aryl
coupling protocol can be a promising alternative for the construction of bi-aryl com-
pounds, due to its salient features, such as simplicity, relatively short and acceptable
reaction times, good-to-excellent yields of the pure products, the use of PEG-400
as a green solvent, the absence of palladium (in any form) in the reaction medium,
and also the use of recoverable and reusable zirconocene-containing magnetically
nanocatalyst. Moreover, it is worthy to note that prepared new and eꢃective diverse
Pd-free catalytic systems for the Suzuki–Miyaura cross-coupling reaction are in the
process in our research group and will be reported in due time.
Acknowledgements We are grateful to the Research Council of Urmia University for partial support of
this research.
Compliance with ethical standards
Conꢁict oꢀ interest The authors declare no conꢁict of interest.
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