Magnetic nanoparticles-supported palladium catalyzed Suzuki-Miyaura cross coupling

Article abstract of DOI:10.1016/j.tetlet.2020.151594

A new magnetic nanoparticles-supported palladium(II) nanomagnetic catalyst (Pd-AcAc-Am-Fe₃O₄?SiO₂) was synthesized and characterized using attenuated total reflectance infrared spectroscopy (ATR-IR), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), energy-dispersive X-ray spectroscopy (EDS), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The nanomagnetic catalyst was used as an efficient catalyst for the Suzuki-Miyaura cross-coupling of various aryl bromides/chlorides/iodides with phenylboronic acid. The effect of varying solvents, base, temperature, reaction time and catalyst amount on the performance of the Suzuki-Miyaura cross-coupling is investigated. The notable advantages of heterogeneous nanomagnetic catalyst are excellent yields, mild reaction conditions, short reaction time, easy magnetic work-up and recyclability. Moreover, the new nanomagnetic catalyst could be easily recovered with an external magnet and reused at least six times without significant loss of its catalytic activity.

Full text of DOI:10.1016/j.tetlet.2020.151594

Journal Pre-proofs
Magnetic Nanoparticles-Supported Palladium catalyzed Suzuki-Miyaura Cross
Coupling
Sandip P. Vibhute, Pradeep M. Mhaldar, Rajendra V. Shejwal, Dattaprasad M.
Pore
PII:
S0040-4039(20)30003-4
DOI:
https://doi.org/10.1016/j.tetlet.2020.151594
TETL 151594
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
5 November 2019
2 January 2020
3 January 2020
Please cite this article as: Vibhute, S.P., Mhaldar, P.M., Shejwal, R.V., Pore, D.M., Magnetic Nanoparticles-
Supported Palladium catalyzed Suzuki-Miyaura Cross Coupling, Tetrahedron Letters (2020), doi: https://doi.org/
1
0.1016/j.tetlet.2020.151594
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Tetrahedron Letters
journal homepage: www.elsevier.com
Magnetic Nanoparticles-Supported Palladium catalyzed Suzuki-Miyaura Cross
Coupling
a,b
a
b
a*
Sandip P. Vibhute , Pradeep M. Mhaldar , Rajendra V. Shejwal , Dattaprasad M. Pore
a
Department of Chemistry, Shivaji University, Kolhapur- 416004, India *E-mail: p_dattaprasad@rediffmail.com
Lal Bahadur Shastri College of Arts, Science and Commerce, Satara., India
b
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A new magnetic nanoparticles-supported palladium(II) nanomagnetic catalyst (Pd-AcAc-Am-
Fe @SiO ) was synthesized and characterized using attenuated total reflectance infrared
3
O
4
2
spectroscopy (ATR-IR), inductively coupled plasma-atomic emission spectroscopy (ICP-AES),
energy-dispersive X-ray spectroscopy (EDS), field-emission scanning electron microscopy (FE-
SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM).
The nanomagnetic catalyst was used as convenient and efficient catalyst for the Suzuki–Miyaura
cross-coupling of various aryl bromides/chlorides/iodides with phenylboronic acid. The effects
of varying solvents, base, temperature, reaction time and catalyst amount on the performance of
the Suzuki– Miyaura cross-coupling reaction were investigated. The notable advantages of this
heterogeneous nanomagnetic catalyst are excellent yields, mild reaction conditions, short
reaction times and easy magnetic work-up and recyclability. Moreover, the new nanomagnetic
catalyst could be easily recovered with an external magnet and could be reused at least six times
without significant loss of its catalytic activity.
Available online
Keywords: Magnetic Nanoparticles , Suzuki-Miyaura, Heterogeneous, Reusability
2
009 Elsevier Ltd. All rights reserved.
1
. Introduction
The palladium-catalyzed Suzuki–Miyaura cross coupling is one of the most valuable synthetic methods for synthesis of biaryls,
which play an important role as a partial structures in pharmaceuticals, natural products, agrochemicals and in the field of engineering
materials such as molecular wires, liquid crystals and conducting polymers [1-9]. Till date, numerous homogeneous as well as
heterogeneous catalysts have been developed for Suzuki–Miyaura cross‐coupling reactions [10–22]. Among these, homogeneous Schiff
base–transition metal complexes have been found to exhibit excellent catalytic activities which inspired researchers to develop several
homogeneous catalysts equipped with Schiff base–transition metal complexes [23–26]. However, a major drawback of homogeneous
catalysts is the difficulty in their separation from the reaction mixture that prohibits recovery and reuse. Current economical factors in
the large‐scale synthesis and environmental concerns compel the scientific community to develop catalysts that would be recyclable and
reusable several times. Hence, huge efforts have been made for the design and development of various heterogeneous catalysts for
Suzuki–Miyaura cross‐coupling. Numerous examples of immobilization of Schiff base–transition metal complexes on various supports,
such as ferrite [27, 28] zeolite [29, 30] polymer [31-33] and clay [34] have been reported. Inorganic matrices show some advantages
over organic supports, such as high thermal, chemical and mechanical stability. The increasing demand for eco‐friendly chemical
processes has stimulated many researchers across the globe to develop heterogeneous catalysts, which can be recovered easily and
reused effectively. Recently, palladium immobilized on the surface of silica was used as a heterogeneous catalyst for the Suzuki-
Miyaura cross-coupling reaction [35]. In continuation of our recent investigation of the application of magnetically recyclable catalysts
in organic transformations,[36] herein we design and synthesize a new nanomagnetic catalyst, a ferrite supported silica coated amine
3 4 2
functionalized Schiff base–palladium(II) complex (Pd-AcAc-Am-Fe O @SiO ) for Suzuki–Miyaura cross‐coupling of various aryl
halides with phenylboronic acid. The synthesized nanomagnetic catalyst was characterized by various spectroscopic and microscopic
techniques.

2
Tetrahedron Letters
O
O
FeCl .6H O
3
2
Urea, NaOH
TEOS, EtOH
NH OH, RT
APTES, EtOH H N
2
Si
O
Fe O
4
Fe O4
Fe O
4
3
3
3
+
5- 90 o
24 h, RT
8
C
4
FeSO .7H O
4
2
Fe O @SiO
Am-Fe O @SiO
3
4
2
3
4
2
O
O
O
O
O
2
O
N
N
O
O
Si
NH2
O
Si
Fe O4
Fe O
4
Pd
3
3
Pd(OAc) , Acetone,
O
2
O
R.T., 6 h
O
Si
O
Am-Fe O @SiO
Pd-AcAc-Am-Fe O @SiO
3 4 2
3
4
2
Scheme 1: Synthetic route towards preparation of catalyst
2
2
. Result and Discussion
.1 ATR-IR:
The attenuated total reflectance infrared spectroscopy was used to characterize the functionality in Fe
3
O
4
, Fe
[Fig. 1]. The presence of stretching vibration band at 555 cm
) [38]. The silica coating of magnetite nanoparticles was confirmed
to
, a significant reduction of the intensity of the Fe-O stretching and bending vibration bands is observed. The characteristic
3 4 2
O @SiO , Am-
-1
Fe
3
O
4
@SiO
2
, AcAc-Am-Fe
3
O
4
@SiO
2
and Pd (II)-AcAc-Am-Fe
3
O
4
@SiO
2
with a slight splitting is attributed to Fe-O bond in magnetite (Fe
3
O
4
by observation of a broad band at 1071 cm−1 which can be assigned to Si-O stretching vibrations. On moving from Fe
O
3
4
Fe
3
O
4
@SiO
2
-1
-1
absorption bands observed at 3362 cm and 1554 cm is due to stretching and bending vibrations of physically adsorbed water and
-1
surface O-H groups. The band at 2927 cm corresponds to the C-H stretching in CH
Fe @SiO . The spectrum of the acetyl acetone grafted over Am-Fe @SiO exhibited a strong band at 1641 cm due to C=N
stretching vibration. This confirms the covalent binding of ligand on the surface of Am-Fe @SiO . On metallation, palladium binds to
2
group of amino-propyl group in functionalized
-1
3
O
4
2
3
O
4
2
3
O
4
2
the bidentate complex and prominent C=N stretching frequency was shifted to lower wave number, indicating strong metal–ligand
interaction.
Fig. 1: ATR-IR analysis of a) Fe
.2 TEM and SEM:
For the investigation of particle size, shape and morphology of the synthesized nanocomposites, transmission electron microscopy
3 4 3 4 2 3 4 2 3 4 2 3 4 2
O , b) Fe O @SiO , c) Am-Fe O @SiO , d) AcAc-Am-Fe O @SiO , e) Pd-AcAc-Am- Fe O @SiO
2
(
TEM) study was conducted. TEM image of final catalyst (Fig. 2a) elucidates the uniform metal binding to the core-shell surface
nanocomposites. The TEM image of recovered catalyst (Fig. 2b) has also been provided to confirm that shape and diffraction pattern
Fig. 2c) confirmed the crystallinity of these nanoparticles and was found to be consistent with XRD results.
(
a
b
c
c
a
b
Fig. 2: TEM images of prepared catalyst. Before reaction (a) 50 nm; after sixth run (b) 50 nm (c) SAED.
Another technique that provides considerable amount of information about the topography of the sample is the scanning electron
microscopic (SEM) analysis. The transition from smooth surface of MNP to spongy surface confirms the successful coating of MNP by
a silica shell (Fig. 3a). The FE-SEM images display spherical morphology of the Pd-AcAc-Am-Fe O @SiO catalyst with slight
3 4 2
aggregation and appear same as that of SMNP, thereby suggesting that surface modification processes did not alter the morphology of
the nano-catalyst. In addition to this, the SEM image of the recovered catalyst indicates that the shape and morphology of the catalyst
remain unaltered (Fig. 3b).

a
b
Fig. 3: SEM images of catalyst a) Before reaction b) After reaction
2
.3 Elemental and compositional analysis:-
Energy dispersive X-ray spectroscopy (EDX) is a powerful tool for accomplishing the elemental analysis of various samples. The
EDX spectrum of Pd-AcAc-Am-Fe O @SiO (Fig. 4) shows the presence of iron, silicon and oxygen atoms which reveal the existence
3 4 2
of a silane shell around the magnetic core material. Apart from these elements, the peaks of nitrogen, carbon and palladium authenticate
the successive surface functionalization, ligand immobilization and metallation of the silica encapsulated magnetite nanoparticles, thus
by confirming the structure of the final nanocatalyst. The amount of Pd also measured by inductively coupled plasma atomic emission
spectrometry (ICP-AES) which was found to be 0.99 wt. %.
Fig. 4: EDX spectrum of catalyst
2
.4 Vibrating Sample Magnetometer:
3 4 2
The magnetic properties of Pd-AcAc-Am-Fe O @SiO were assessed using a vibrating sample magnetometer (VSM) (Fig.5). The
curves exhibit an extremely interesting phenomenon showing a decrease in the values of the saturation magnetization (Ms) of Pd-AcAc-
Am-Fe @SiO is 34.00 emu/g in comparison with the bulk magnetite nanomaterials that typically show a saturation magnetization
3
O
4
2
value of 92 emu/g. It could be reasoned that the silica coating and the immobilization of various species onto the magnetic nanosupport
cause a reduction in the surface moments of the individual particles, eventually resulting in a decrease in the net magnetism possessed
by these materials [39]. It is believed that however, despite the lowering of the Ms values, the application of the surface modified
nanocomposites remains unaffected as they show a fast response to an applied magnetic field by getting quickly attracted to an external
magnet, suggesting that the synthesized nanocatalyst possesses good magnetism and redispersibility.
Fig. 5: VSM spectrum of catalyst
2
.5 Catalytic Activity of Pd-AcAc-Am- Fe
3 4 2
O @SiO in Suzuki–
Miyaura Cross-Coupling Reactions:
After full characterization of the synthesized Pd-AcAc-Am-
@SiO nanomagnetic catalyst with spectroscopic and
Fe
3
O
4
2
microscopic methods, its catalytic potential was investigated as a
magnetically separable nanomagnetic catalyst in Suzuki–Miyaura cross
coupling reactions. The Suzuki–Miyaura cross-coupling reaction is one
the most important method for C-C bond formation in organic
transformations. The Suzuki–Miyaura cross coupling reaction is used
various organic reactions and therefore it now belongs to an essential
set of palladium catalyzed cross coupling reactions. Thus, the catalytic
of
in
potential of the synthesized nanomagnetic catalyst was explored in Suzuki–Miyaura cross coupling reactions. The reaction conditions
such as solvent, base, temperature, amount of catalyst loading were optimized for a model Suzuki–Miyaura cross coupling reaction of
iodobenzene with phenylboronic acid. Considering the key role of base in the formation of active palladium intermediates and
promoting transmetallation during the catalytic cycle of Suzuki–Miyaura cross– coupling reaction, [40] different bases including
sodium/potassium inorganic salts and organic base were screened (Table 1, Entries 1–11). It was found that, K CO was superior and
2 3
giving an excellent yield (Table 1, Entry 6). Likewise, we did an experiment in the absence of base, no cross–coupling product was
observed, which confirmed the necessity of base for the smooth Suzuki–Miyaura cross–coupling reaction (Table 1, Entry 8).

4
Tetrahedron Letters
Table 1. Optimization of base and amount of catalyst for
Suzuki coupling reaction
2 3
Screening of solvents was carried out employing K CO as a base
with toluene, dioxane, ethanol, THF, Acetonitrile, DMF and
DMF:Water mixed solvent system. We observed that yield of the
desired product is increased to 98 % in DMF:Water system (8:2, v/v)
Yield (%)a
Entry
Catalyst (mg)
Base
NaOH
KOH
1
2
3
4
5
6
7
8
9
30
30
30
30
30
30
30
30
40
20
15
75
78
59
52
85
98
88
(
Table 2, entry 10). Presence of water in a reaction media increases
NaOAc
solubility of the bases, which is responsible for the activation of
boronic acid resulting in enhancing the rate of the reaction in aqueous
medium [41]. It is noteworthy that, the reaction only in water did not
proceed at all probably due to scanty solubility of the reactants in the
water (Table 2, Entry 2).
N(C
PO
K CO
2
H
5
)
3
K
3
4
2
3
Na
2
CO
--
K CO
3
After attaining the optimal reaction conditions, we then examined
the applicability of the present catalytic system to the Suzuki–Miyaura
cross–coupling of various aryl halides and different aryl boronic acids
No reaction
2
3
98
89
84
1
1
0
1
K
K
2
CO
CO
3
(
Table 3). A wide range of electronically and structurally diverse aryl
2
3
iodides, bromides and chlorides were readily coupled with different
substituted aryl boronic acids in excellent yields. It was observed that,
the reaction of aryl halides with electon deficient aryl boronic acid
took slightly longer time compared to those of the electron–neutral
and electron–rich boronic acids (Table 3, Entries 6-8). Various aryl
*
Reaction conditions: Iodobenzene (1mmol), phenylboronic
acid (1.2 mmol), base (3 mmol), catalyst (Pd-acac-am-
Fe @SiO ) (0.030 g, 0.28 mol% Pd), temp.= 80 °C, 2 h;
solvent = DMF: Water (8:2) 5 mL, Isolated yield
3
O
4
2
a
halides bearing electron–withdrawing groups such as nitro, cyano, aldehyde, acetyl moieties, and electron donating groups such as
methyl and methoxy moieties react with different substituted aryl boronic acids to afford biaryls in excellent yields (Table 3, Entries 1–
1
1). It is noteworthy that less activated aryl chlorides bearing either electron-donating or electron-withdrawing substituent afforded
corresponding products in excellent yields (Table 3, Entries 12-13).
Further to extend the scope of the catalytic system, we next employed boronic acids possessing heterocyclic moiety as coupling
partners for Suzuki–Miyaura cross coupling. Due to the low reactivity of substituted heterocycle [42-44] moderate yield of the target
product was obtained (Table 3, Entries 16-18).

Table 3. Combinatorial library of biaryls synthesised by Suzuki–Miyaura coupling
B(OH) 2
X
Pd-AcAc-Am-Fe O @SiO
2
3
4
R
+
R'
DMF: Water (8:2), K CO
2
3
R'
R
o
8
0
C
Time Yieldb TON
TOF
(h )
Aryl boronic acid
Aryl halide
Product
Entry
-
1
(h)
(%)
B(OH) 2
X
R
R = H
R = H
R'
R'
R
1
R’= 4-H, X= I
R’= 4-H, R= H
1
96
342
342
342
350
342
342
285
328
339
335
321
321
307
342
342
342
350
342
171
95
R = H; R’= 4-OCH
R = OCH ; R’= 4-OCH
R = H; R’= 4-CN
R =3CH ; R’= 4-CN
R = H; R’= 4-NO
3
2
3
R’= 4-OCH
R’= 4-OCH
3
3
, X= I
, X= I
1
1
96
96
R = OCH
R = H
3
3
3
R’= 4-CN, X= I
R’= 4-CN, X= I
4
5
1
1
98
96
R =3-CH
3
3
6
7
8
9
R = H
R’= 4-NO
2
, X= I
, X= I
2
2
3
3
1
1
2
1
3
96
80
92
95
94
90
90
86
R = H
R’= 4-COCH
3
R = H; R’= 4-COCH
R = H; R’= 4-CHO
3
R = H
R’= 4-CHO, X= I
R’= 4-Cl, X= I
109
339
335
160
321
102
R = NH
R = H
2
R = NH
2
; R’= 4-Cl
1
1
1
1
0
1
2
3
R’= 4-CH
R’= 4-OCH
3
, X= I
, X= Br
R = H; R’= 4-CH
3
R = H
3
R = H; R’= 4-OCH
R’= 4-H, R= H
3
R = H
R’= 4-H, X= Cl
R = NH
2
R’= 4-H, X= Cl
R = NH
2
; R’= 4-H
B(OH)2
I
1
1
4
5
1
1
80
96
286
286
342
B(OH)2
I
3
42
I
B(OH)
X
2
X
R
R
1
1
6
7
X= -S
R= 4-H, X= -I
R= 4-H, X= -I
R= 4-H, X= S
R= 4-H, X= O
2
2
89
90
318
321
159
160
X= O
O
B(OH)2
O
2
89
318
159
1
8
O
Br
O
a
3 4 2
Reaction conditions: aryl halide (1mmol), phenylboronic acid (1.2 mmol), Pd-acac-Am-Fe O @SiO (0.030 g, 0.28 mol% Pd),
K CO (3 mmol), DMF:water (8:2), 5 mL, temp = 80 C; Isolated yield.
2 3
o
b

6
Tetrahedron
Table 2. Optimization of Solvent for Suzuki cross coupling*
The comparative study of catalytic activity of Pd-AcAc-Am-
@SiO with the various supported heterogeneous palladium
Pd-AcAc-Am-Fe O @SiO
3
4
2
B(OH) 2
+
I
Base, Solvent
Fe
3
O
4
2
o
80
C
catalysts is depicted in Table 4. It is primarily observed that many of
the supported catalysts exhibit the catalytic activity at higher
Yield (%)a
o
Entry
Solvent
temperature (90 to 110 C) as compared to Pd-AcAc-Am-
Fe
3
O
4
@SiO
2
furnishing lower yields (Table 4, entries 2-4). In
, Fe @SiO -Pd and
1
2
Ethanol
Water
50
NR
addition, some of the catalysts viz Pd@Fe
Pd@SMP revealed high yields at ambient temperature but require
far longer reaction time (12 h) as compared to present protocol
3
O
4
3
O
4
2
3
4
5
6
Acetonitrile
THF
55
60
68
72
3 4 2
(Table 4, entries 5-7). Moreover, Pd-AcAc-Am-Fe O @SiO is
more proficient compared to the MSN-IPr and FeS@EP–AG–Pd
with respect to reaction time (Table 4, entries 8-9). Therefore, Pd-
AcAc-Am-Fe O @SiO is found to be superior as compared to other
3 4 2
reported catalysts producing high yields (87–98%) in short reaction
time. It is noteworthy to mention that, unlike in other reported
protocols, the catalyst could easily be recovered by applying an
external magnet thereby avoiding loss of catalyst during attrition.
Dioxane
Toulene
DMF
7
8
9
88
82
91
DMF: Water (5:5)
DMF: Water (7:3)
1
0
DMF: Water (8:2)
98
*
Reaction conditions: Iodobenzene (1mmol), phenylboronic
CO (3 mmol), catalyst (Pd-acac-am-
) (0.030g, 0.28 mol% Pd), temp.= 80 °C, 2 h;
Table 4: Comparison of catalytic efficiency of Pd-AcAc-Am-
Fe O @SiO with reported catalysts for Suzuki-Miyaura coupling
3 4 2
acid (1.2 mmol), base K
Fe @SiO
solvent = 5 mL, NR= No Reaction Isolated yield
2
3
3
O
4
2
Sr.
No.
1
Catalyst
Temp
0C
Solvent
Time
(h)
1
Yield
%
Ref.
a
Pd-AcAc-Am-
Fe @SiO
80
DMF:H
DMF:H
2
O
O
96
This
work
3
O
4
2
2
3
Maghemite–Pd
MNP-
110
100
2
1
5
90
92
45
46
DMF
di(2pyridyl)methanol–
Pd
4
Graphene-
90
----
0.5
90
47
Fe
Fe
3
3
O
4
4
@SiO
2
2
@Pd
-Pd
5
6
O
@SiO
RT
45-
EtOH
12
12
90
91
48
49
Pd@Fe
3
O
4
MeOH
6
0
7
8
9
Pd@SMP
MSN-IPr
80
80
Dioxane
iPrOH
15
2
96
90
50
51
FeS@EP–AG–Pd
SBA15/AO/Pd(0)
50
50
Water
2
1
99
98
52
53
1
0
2
H O:EtOH
One of the most important factors in heterogeneous catalysis is catalyst recovery and recycling. The newly synthesized Pd-AcAc-
Am-Fe @SiO nanomagnetic catalyst was successfully recovered by applying an external magnetic field washed thoroughly with
3
O
4
2
ethanol and distilled water and dried at 50 °C for 6 h and reused for next run. It was observed that there was no change in catalytic
activity up to 6 recycles without any noticeable loss in yield (Fig. 6). Recycled nanomagnetic catalyst was characterized using SEM and
TEM analysis. No significant change in morphology as well as particle size of the nanocatalyst was found.
Fig. 6: Reusability of catalyst

Conclusion:
3 4 2
A new reusable Pd-AcAc-Am-Fe O @SiO nanomagnetic catalyst was successfully prepared and characterized using ATR‐IR,
TEM, FE-SEM, EDX, ICP‐AES and VSM. The main advantages of the catalyst are simplicity, selectivity, eco-friendliness and ease of
recovery using an external magnetic field. The recovered catalyst can be reused up to six cycles without significant loss of catalytic
activity. The developed protocol offers many advantages such as broad substrate scope, functional group tolerance, short reaction times,
excellent yields, catalyst reusability, etc. making it compatible for industrial scale application.
Acknowledgement:
One of the authors DMP grateful to acknowledge, Shivaji University, Kolhapur for Financial Assist through Research Strengthening
Scheme. [SU/C&U.D.Section/89/1386].
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Tetrahedron
Graphical Abstract
Magnetic Nanoparticles-Supported Palladium catalyzed Suzuki-Miyaura
Cross Coupling
a,b
a
b
a*
Sandip P. Vibhute , Pradeep M. Mhaldar , Rajendra V. Shejwal , Dattaprasad M. Pore
aDepartment of Chemistry, Shivaji University, Kolhapur- 416004, India *E-mail: p_dattaprasad@rediffmail.com
bLal Bahadur Shastri College of Arts, Science and Commerce, Satara., India
DMF : H O
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Highlights
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The functionalized Fe O MNPs were synthesized and elucidated by various
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Characterization techniques.
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Magnetically induced Suzuki-Miyaura cross coupling at ambient condition.
Low palladium loading was used in the reaction.
Wide functional group compatibility, moderate to excellent yields, simple workup.

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Magnetic nanoparticles could be recovered using an external magnet and reused for
several cycles.
SHIVAJI UNIVERSITY, KOLHAPUR
DEPARTMENT OF CHEMISTRY
UGC-SAP And dST – FIST SPonSored
Prof. (Dr.) Dattaprasad M. Pore
Vidyanagar,
Professor
Kolhapur-416004,
Maharashtra, INDIA
Phone: (0) (0231) 2609161/9164
Fax: +91-0231-2609000
Email: p_dattaprasad@rediffmail.com
To,
The Editor
Tetrahedron Letters
Manuscript title: “Magnetic Nanoparticles-Supported Palladium catalyzed Suzuki-Miyaura Cross
Coupling”
A new magnetic nanoparticles-supported palladium(II) nanomagnetic catalyst (Pd-AcAc-Am-
Fe O @SiO ) was synthesized and characterized using attenuated total reflectance infrared spectroscopy
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2
(ATR-IR), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), energy-dispersive X-ray
spectroscopy (EDS), field-emission scanning electron microscopy (FE-SEM), transmission electron
microscopy (TEM) and vibrating sample magnetometer (VSM). The nanomagnetic catalyst was used as
convenient and efficient catalyst for the Suzuki–Miyaura cross-coupling of various aryl
bromides/chlorides/iodides with phenylboronic acid. The effects of varying solvents, base, temperature,
reaction time and catalyst amount on the performance of the Suzuki– Miyaura cross-coupling reaction were
investigated. The notable advantages of this heterogeneous nanomagnetic catalyst are excellent yields, mild
reaction conditions, short reaction times and easy magnetic work-up and recyclability. Moreover, the new
nanomagnetic catalyst could be easily recovered with an external magnet and could be reused at least six
times without significant loss of its catalytic activity.
Thus, we believe this manuscript deserves to be published in “Tetrahedron Letters” and request you
to consider our manuscript favorably for publication in your esteemed journal.

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Tetrahedron
Prof. (Dr.) D. M. Pore