An Fe3O4@SiO2/Schiff base/Cu(ii) complex as an efficient recyclable magnetic nanocatalyst for selective mono: N-arylation of primary O-alkyl thiocarbamates and primary O-alkyl carbamates with aryl halides and arylboronic acids

Article abstract of DOI:10.1039/c9nj00028c

An efficient, convenient and novel method for the selective mono N-arylation of primary O-alkyl thiocarbamates and primary O-alkyl carbamates with aryl halides and arylboronic acids in the presence of a recyclable magnetic Cu(ii) nanocatalyst is described. A variety of mono N-arylated O-alkyl thiocarbamates and O-alkyl carbamates were prepared in good to excellent yields with a broad range of aryl coupling partners. The magnetic nanocatalyst can be easily recovered with an external magnetic field and reused at least five times without noticeable leaching or loss of its catalytic activity. This cost-effective and eco-friendly methodology has some other advantages, such as easy preparation of the catalyst, simple workup procedure, and easy purification, which makes this protocol interesting for the users in various fields of pharmacology and biotechnology systems.

Full text of DOI:10.1039/c9nj00028c

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
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Fe3O4@SiO2/Schiff base/Cu(II) Complex as an Efficient Recyclable
Magnetic Nanocatalyst for Selective Mono N-Arylation of Primary
O-Alkyl Thiocarbamates and Primary O-Alkyl Carbamates with
Aryl Halides and Arylboronic Acids
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Ali Reza Sardarian,*a Iman Dindarloo Inalooa and Milad Zangiabadia
www.rsc.org/
An efficient, convenient and novel method for the selective mono N-arylation of primary O-alkyl thiocarbamates and
primary O-alkyl carbamates with aryl halides and arylboronic acids in the presence of recyclable magnetic Cu(II)
nanocatalyst is described. A variety of mono N-arylated O-alkyl thiocarbamates and O-alkyl carbamates were prepared in
good to excellent yields with a broad range of aryl coupling partners. The magnetic nanocatalyst can be easily recovered
with an external magnetic field and reused at least five times without noticeable leaching or loss of its catalytic activity.
This cost effective and eco-friendly methodology has some other advantages, such as easy preparation of the catalyst,
simple work‐up procedure, and easy purification, which makes this protocol interesting for the users in various fields of
pharmacology and biotechnology systems.
Introduction
Because of an important role of N-substituted
O-thiocarbamates and carbamates in many areas of industry
and science including biology,1 agriculture,2 medicinal
chemistry,3 coatings and materials science,4 the selective
synthesis of these compounds is the subject of an important
challenge in organic chemistry.5
These N-substituted thioesters and esters of carbamic acid,
in addition to widely as insecticides,6 pesticides7 and drug
design,8 they show a wide range of biological activity like
herbicides,9 antibacterial agents,10 antimicrobial agents,11
11b,
antiviral agents,12 anti-HIV,13 anticancer14 and antitumor.
13f, 15
In particular, mono N-substituted O-alkyl thiocarbamates
and O-alkyl carbamates are found in numerous the
therapeutically relevant compounds, including approved
pharmaceuticals such as flupirtine, retigabine, albendazole and
NNB (O-[2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl] (4-
bromophenyl) thiocarbamate) that are depicted in Figure 1.16
These compounds are appearing in organic chemistry,
especially as amine protecting groups in peptide synthesis,17
materials and polymer chemistry,18 and also as a valuable
intermediate for the synthesis of other useful products19-23
such as thiols via Newman–Kwart rearrangement,20
Figure 1. Some biologically active mono N-substituted O-alkyl
thiocarbamates and O-alkyl carbamates
The most common methods for the synthesis of these
compounds have been using toxic and harmful chemicals such
as
phosgene,24
thiophosgene,25
isocyanate26
and
To avoid the use of these hazardous
27
isothiocyanate.26c,
reagents, several methods have also been reported.28,
However, these methodologies may present some
disadvantages such as multi-step procedures, high
temperature or pressure, high cost and unstable reagents,
large excess amounts of carbonyl and thiocarbonyl sources,
non-selective reactions and narrowed scope of amines.29
After the successful efforts for the synthesis of new
compounds with N-arylation reactions in the presence of
transition metals catalysts such as Pd, Cu, Ni, Fe, and etc.30
During the past two decades, trying to synthesize of N-aryl
carbamates by using transition metals as a catalyst has
attracted much interest.31-33 However, these new protocols
29
organocatalysts,21
assemblies.23
dendrimers22
and
supramolecular
a. Chemistry Department, College of Sciences, Shiraz University, Shiraz 71946-84795,
Iran.
E-mail address: sardarian@shirazu.ac.ir
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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After preparation of Cu(II)-MNPS catalyst, its catalytic activity
rely heavily on expensive ligands or bases and reactive
functional groups, which usually require cumbersome
synthetic procedures.31 Also, inability to recover the transition
metals used as the catalyst is one of the main drawbacks of
these methods.32-33 Despite the broad spectrum of coupling
partners that have been described, we are unaware of any
reports of the transition metal-catalyzed selective N-arylation
of O-alkyl thiocarbamates even with the versatility of this
functional group in synthesis.
was tested in N-arylation of primary O-alkyl thiVoiecwaArrbtiaclme Oantlienes
DOI: 10.1039/C9NJ00028C
reaction. In our first phase of screening experiment, 1 mmol of
O-propyl thiocarbamate (1a) and 1 mmol of iodobenzene (3a)
were used as the model substrates to optimize reaction media
factors including the amount of catalyst, bases, solvents, and
reaction temperatures (Table 1).
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Table 1. Optimization of the reaction parameters for the
preparation of O-propyl phenylthiocarbamate (4a).a
Based on the growing demand for environmental- benign
technologies that are operating in accordance with the
principles of green chemistry in the last few years, some
research groups designed new clean, safe, sustainable and
selective methodologies for the synthesis of the different class
of organic compounds with silica-based magnetically
retrievable core-shell nanocatalysts.34-35 Following our ongoing
studies for designing and employing new reusable magnetic
nanocatalysts in synthesis of the important organic
chemistry,35 herein for the first time, we report the utilization
of Fe3O4@SiO2/Schiff Base/Cu(II) Complex as a magnetic
nanocatalyst for selective mono N-arylation of O-alkyl
thiocarbamates and O-alkyl carbamates through coupling
reaction with aryl halides and arylboronic acids as coupling
partners (Scheme 1).
Entry
Solvent
Base
(mmol)
Catalyst
(mol %)
T
(°C)
Yield
(%)b
1
2
3
4
5
6
7
8
H2O
Toluene
DMF
CH3CN
CH2Cl2
Ethanol
Methanol
Dioxane
DMSO
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
NaOBut(1)
NaOBut(1)
NaOBut(1)
NaOBut(1)
NaOBut(1)
NaOBut(1)
NaOBut(1)
NaOBut(1)
NaOBut(1)
KOH(1)
KHCO3(1)
KOAc(1)
CsF(1)
K3PO4(1)
K2CO3(1)
CsCO3(1)
Et3N(1)
Pyridine(1)
None
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
None
0.25
0.75
reflux
100
100
0
75
Trace
reflux Trace
reflux
reflux
reflux
100
100
100
100
100
100
100
100
100
100
100
100
100
100
25
50
70
80
90
110
120
100
100
100
0
0
0
68
20
0
9
10
11
12
13
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18
19
20
21
22
23
24
25
26
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29
30
31
0
0
12
Trace
10
53
0
Scheme 1. N-Monoarylation of primary O-alkyl thiocarbamates and
O-alkyl carbamates
Results and discussion
0
0
The retrievable magnetite (Fe3O4) silica-based copper(II)
nanocatalyst(Cu(II)-MNPS) was synthesized through the
protocol which was reported in 2012 by our research group.35a
Scheme 2 concisely describes the synthetic procedure of the
catalyst.
NaOBut(1.5)
NaOBut(2)
NaOBut(1.5)
NaOBut(1.5)
NaOBut(1.5)
NaOBut(1.5)
NaOBut(1.5)
NaOBut(1.5)
NaOBut(1.5)
NaOBut(1.5)
NaOBut(1.5)
NaOBut(1.5)
85
84
Trace
38
57
61
78
85
84
0
71
83
a
Reaction conditions: O-propyl thiocarbamate (1 mmol),
iodobenzene (1 mmol), base and catalyst in solvent (2 mL),
under an atmosphere of air for 3 h.
b Isolated yield.
As shown in Table 1, the efficiency of model reaction was
explored in with several common solvents, such as H2O, DMF,
DMSO, dioxane, toluene, dichloromethane, acetonitrile,
Scheme 2. Synthetic procedure of Fe3O4@SiO2/Cu(II) complex.
2 | J. Name., 2012, 00, 1-3
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methanol and ethanol, and in the presence of bases, such as thiocarbamate, as
a
sterically hindered O-tVeierwtiaArrtyicle Oanlklinyel
KOH, KHCO3, KOAc, CsF, K3PO4, CsCO3, K2CO3, NaOBut, pyridine thiocarbamate (Table3, entry 4g). O-Benzyl thiocarbamates
and triethylamine at different temperatures. According to (Table3, entries 4j and 4k), which are widely used as the
these data, the presence of catalyst and base are necessary protecting groups in organic synthesis, and O-allyl
and critical for this reaction (Table 1, entries 19 and 29) and thiocarbamate were also carried out this reaction effectively
the best efficiency was provided when the model reaction was (Table3, entry 4i). Among halobenzenes, iodobenzene
run in toluene and in the presence of NaOBut (1.5 mmol) and exhibited greater reactivity compared to that of
DOI: 10.1039/C9NJ00028C
Cu(II)-MNPS (0.5 mol%) at 100 OC (Table 1, entry 20).
bromobenzene and chlorobenzene was the most unreactive
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The effect of other catalysts, such as Cu(OAc)2, CuO2, CuCl, one and afforded the cross-coupled products in less than 10%
CuBr, CuI, NiCl2, Fe3O4, Fe3O4/Cu(OAc)2 and Schiff Base/Cu(II) yield even in longer reaction times. Phenylboronic acid was
Complex were explored on the model reaction instead of also
a suitable substrate for N-arylation of primary
Cu(II)-MNPS. On the basis of results exhibited in Table 2, the O-thiocarbamates. Although primary O-aryl thiocarbamates
reaction was led to the desired product in the presence of all underwent the N-arylation reaction with halobenzenes (I, Br,
of the Cu catalysts checked but in low yields after 3 hours at Cl) and phenylboronic acid, on the base of TLC monitoring, but,
100 OC. Using the mixture of Fe3O4 and Cu(OAc)2 as the due to the instability of the corresponding products, their
catalyst was conducted to only 13% yield (Table 2, entry 9). purification was not possible by chromatographic procedures,
Even using Schiff base/Cu(II) complex as homogeneous catalyst which are in agreement to the report of Buchwald and co-
under the optimized reaction conditions, did not result in a workers.32a
Table 3. Coupling of primary O-alkyl thiocarbamates 1 with
better performance than Cu(II)-MNPS (Table 2, entries 10 and
11).
halobenzenes and phenylboronic acid.a
Table 2. The screening of catalytic reactivity of several
catalysts on N-arylation of O-propyl thiocarbamate (1a).a
4b
4c
4a
Catalyst
Yield (%)b
X: I, 83%b, 3h
X: Br, 78%b, 3h
X: Cl, 09%b, 8h
X: B(OH)2,78%b, 3h
X: I, 82%b, 3h
X: Br, 75%b, 3h
X: Cl, 07%b, 8h
X: B(OH)2,78%b, 3h
X: I, 85%b, 3h
X: Br, 79%b, 3h
X: Cl, 08%b, 8h
X: B(OH)2,77%b, 3h
Entry
1
2
3
4
Cu(OAc)2
CuO2
CuCl
CuBr
CuI
12
Trace
Trace
12
15
5
NiCl2
Fe3O4
0
0
0
13
84
85
4d
6
7
8
9
10
11
4e
4f
X: I, 88%b, 3h
X: Br, 80%b, 3h
X: Cl, 09%b, 8h
X: B(OH)2,79%b, 3h
X: I, 80%b, 3h
X: Br, 74%b, 3h
X: Cl, 06%b, 8h
X: B(OH)2,73%b, 3h
X: I, 79%b, 3h
X: Br, 74%b, 3h
X: Cl, 05%b, 8h
X: B(OH)2,72%b, 3h
Fe3O4@SiO2
Fe3O4/ Cu(OAc)2
Schiff base/Cu(II) Complex
Fe3O4@SiO2/Schiff base Cu(II)
Complex (Cu(II)-MNPS)
a
4h
4g
4i
Reaction conditions: O-propyl thiocarbamate (1 mmol),
X: I, 81%b, 3h
X: I, 80%b, 3h
X: Br, 74%b, 3h
X: Cl, 06%b, 8h
X: B(OH)2,75%b, 3h
X: I, 86%b, 3h
X: Br, 80%b, 3h
X: Cl, 09%b, 8h
X: B(OH)2, 81%b, 3h
iodobenzene (1 mmol), NaOBut (1.5 mmol) and catalyst (0.5
X: Br, 79%b, 3h
X: Cl, 09%b, 8h
X: B(OH)2, 80%b, 3h
mol%) in toluene (2 mL), 100 OC under an atmosphere of air
for 3 h.
b Isolated yield.
With optimal conditions in hand, further investigations into
the substrate scope of this reaction process were performed. A
variety of available primary O-alkyl thiocarbamates 1 and
primary O-alkyl carbamates 2 were coupled with aryl halides (I,
Br, Cl) or arylboronic acid 3 to afford the corresponding
N-mono substituted O-alkyl thiocarbamates 4 and N-mono
substituted O-alkyl carbamates 5.
As shown in Table 3, most of examined primary O-alkyl
thiocarbamate substrates 1 showed a similar performance.
This procedure was also effective for secondary O-alkyl
thiocarbamates (Table 3, entries 4e, 4f, and 4h), O-tert-butyl
4j
4l
4k
X: I, 82%b, 3h
X: Br, 79%b, 3h
X: Cl, 08%b, 8h
X: B(OH)2,80%b, 3h
X: I, 83%b, 3h
X: Br, 78%b, 3h
X: Cl, 08%b, 8h
X: B(OH)2,79%b, 3h
X: I, 75%b, 3h
X: Br, 74%b, 3h
X: Cl, 06%b, 8h
X: B(OH)2,70%b, 3h
a
Reaction conditions: O-alkyl thiocarbamates (1 mmol),
halobenzenes or phenylboronic acid (1 mmol), NaOBut (1.5
mmol) and catalyst (0.0250 g, 0.5 mol%) in toluene (2 mL), 100
OC under an atmosphere of air.
b Isolated yield.
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Because of the results achieved in N-arylation of primary primary O-propyl thiocarbamate (1a) and primVairewy AOrtic-plerOonplinyel
O-alkyl thiocarbamates 1 for determination the scope of this carbamate (2a) that the related results were collected in Table
DOI: 10.1039/C9NJ00028C
protocol, the catalytic activity of Fe3O4@SiO2/Schiff base/Cu(II) 5. The reaction was equally effective for both electron
complex was studied in N-arylation of primary O-alkyl donating and electron withdrawing groups in aryl iodides.
carbamates 2 by halobenzenes and phenylboronic acid under Among ortho-, meta- and para- iodo toluene, it was ortho-
the optimized conditions achieved in N-arylation of O-alkyl isomer that carried out the N-arylation reaction in low yield
thiocarbamates 1 (Table 4). The data exhibited in Table 4 (Table 5, entries 4o and 5o) because of probably the steric
confirmed the efficient activity of the catalyst and the order of effect of the methyl group. Fortunately, 3-iodothiophene, as a
activity of halobenzenes and phenylboronic acid was appeared heteroaryl iodide, underwent the N-arylation reaction
to be I>Br≈ B(OH)2>> Cl, which is the same as their activity in efficiently and provided the corresponding products in good
N-arylation of primary O-alkyl thiocarbamates 1. In addition, a yields (Table 5, entries 4t and 5t).
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Table5. Copper-catalyzed C-N cross-coupling of O-propyl
thiocarbamate (1a) and O-propyl carbamate (2a) with aryl
iodides a
wide array of primary O-alkyl carbamates 2 was subjected to
this reaction and the corresponding products were obtained in
good to excellent yields.
Table 4. Coupling of primary O-alkyl carbamates 2 with
halobenzenes and phenylboronic acida
4m (X: S), 82%b, 3h
5m (X: O), 89%b, 3h
4n (X: S), 80%b, 3h
5n (X: O), 87%b, 3h
4a (X: S), 85%b, 3h
5a (X: O), 94%b, 3h
5b
5c
5a
X: I,93%b, 3h
X: I,92%b, 3h
X: I,94%b, 3h
X: Br, 82%b, 3h
X: Cl,09%b, 8h
X: B(OH)2, 88%b, 3h
X: Br, 87%b, 3h
X: Cl,07%b, 8h
X: B(OH)2, 88%b, 3h
X: Br, 88%b, 3h
X: Cl,08%b, 8h
X: B(OH)2,89%b, 3h
4p (X: S), 84%b, 3h
5p (X: O), 88%b, 3h
4o (X: S), 46%b, 3h
5o (X: O), 51%b, 3h
4q (X: S), 85%b, 3h
5q (X: O), 93%b, 3h
5d
5e
5f
X: I,95%b, 3h
X: I,88%b, 3h
X: I, 87%b, 3h
X: Br, 84%b, 3h
X: Cl,08%b, 8h
X: B(OH)2, 85%b, 3h
4s (X: S), 81%b, 3h
5s (X: O), 94%b, 3h
4t (X: S), 80%b, 3h
5t (X:O), 89%b, 3h
4r (X: S), 83%b, 3h
5r (X: O), 93%b, 3h
X: Br,90%b, 3h
X: Cl,09%b, 8h
X: B(OH)2,89%b, 3h
X: Br,79%b, 3h
X: Cl,08%b, 8h
X: B(OH)2, 85%b, 3h
4u (X: S), 86%b, 3h
5u (X: O), 92%b, 3h
4v (X: S), 84%b, 3h
5v (X: O), 90%b, 3h
5h
5g
5i
X: I,90%b, 3h
X: I, 88%b, 3h
X: Br,79%b, 3h
X: Cl,06%b, 8h
X: B(OH)2,80%b, 3h
X: I,94%b, 3h
a
Reaction conditions: O-propyl thiocarbamate or O-propyl
X: Br, 88%b, 3h
X: Cl,08%b, 8h
X: B(OH)2, 89%b, 3h
X: Br, 82%b, 3h
X: Cl,09%b, 8h
X: B(OH)2, 88%b, 3h
carbamate (1 mmol), aryl iodides (1 mmol), NaOBut (1.5 mmol)
and catalyst (0.0250 g, 0.5 mol%) in toluene (2 mL), 100 OC
under an atmosphere of air.
b Isolated yield.
5j
5l
5k
Furthermore, to check chemoselectivity of the protocol,
the reaction between 1-bromo-4-iodobenzene with O-propyl
thiocarbamate (1a) and O-propyl carbamate (2a) were
investigated under optimized condition. The result of this
study indicated that the C-N coupling reaction has been taken
place only on the carbon atom bearing iodine and only
O-propyl (4-bromophenyl)thiocarbamate and O-propyl
(4-bromophenyl)carbamate were prepared respectively (Table
6, entry 1A). Then the same reaction was performed between
1-chloro-4-iodobenzene with O-propyl thiocarbamate (1a) and
O-propyl carbamate (2a). In these cases, only the
corresponding O-propyl (4-chlorophenyl)thiocarbamate and
O-propyl (4-chlorophenyl)carbamate were obtained (Table 6,
entry 2B). Finally, the reaction of O-propyl thiocarbamate (1a)
X: I,90%b, 3h
X: I,93%b, 3h
X: I, 89%b, 3h
X: Br, 82%b, 3h
X: Cl,05%b, 8h
X: B(OH)2, 88%b, 3h
X: Br, 81%b, 3h
X: Cl,09%b, 8h
X: B(OH)2,89%b, 3h
X: Br, 86%b, 3h
X: Cl,08%b, 8h
X: B(OH)2,91%b, 3h
a
Reaction conditions: primary O-alkyl carbamates (1 mmol),
halobenzenes or phenylboronic acid (1 mmol), NaOBut (1.5
mmol) and catalyst (0.0250 g, 0.5 mol%) in toluene (2 mL), 100
OC under an atmosphere of air.
b Isolated yield.
For determination of generality of the methodology, the
variety of aryl iodides with electron-releasing and electron-
withdrawing substitutions were utilized for N-arylation of
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and O-propyl carbamate (2a) with 1-bromo -4-chlorobenzene butyrthioamide (6) (1mmol) reacted with iodobenzene
were examined and as it is exhibited in Table 6 only the (1mmol) in the presence of the catalyst. As it is depicted in
O-propyl (4-chlorophenyl)thiocarbamate and O-propyl scheme 4, analysis of the reaction mixture revealed that
(4-chlorophenyl)carbamate were obtained (Table 6, entry 3B). butyrthioamide (6) has remained unchanged and only O-propyl
These results indicate excellent chemoselectivity and the C-N thiocarbamate (1a) underwent selectively the C-N coupling.
coupling reaction have occurred only on the carbon atom This might be again due to the stronger nitrogen
View Article Online
DOI: 10.1039/C9NJ00028C
bears less electronegative halogen atom.
Table 6. Chemoselectivity of the C-N coupling reaction of aryl
halides a
nucleophilicity in O-alkyl thiocarbamates 1 than alkyl
thioamides 6.
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Scheme 4. Reactivity of O-propyl thiocarbamate (1a) and
butyrthioamide (6) toward N-arylation reaction
Product A
(Yield %)b
Product B
(Yield %)b
Product C
(Yield %)b
Entry
1
Substrate
X
However, in the reaction between O-propyl thiocarbamate
(1a) (1mmol) and iodobenzene (1mmol) in the presence of
propylamine (7a) as a competitive partner, no selectivity was
observed. More specifically, they underwent the coupling
reaction and gave similar yields (Scheme 5). So it can be
concluded that O-alkyl thiocarbamates 1 are more reactive
than thioamides in this procedure but they have no superiority
over aliphatic amines.
S
O
84%
93%
-
-
0%
0%
S
O
-
-
86%
92%
0%
0%
2
3
S
O
0%
0%
79%
83%
-
-
a
Reaction conditions: O-propyl carbamate or O-propyl
thiocarbamate (1 mmol), dihalobenzenes (1 mmol), NaOBut
(1.5 mmol) and catalyst (0.0250 g, 0.5 mol%) in toluene (2 mL),
100 OC under an atmosphere of air for 3 h.
b Isolated yield.
Scheme 5. Chemoselectivity study of the C-N coupling reaction
between O-propyl thiocarbamate (1a) and n-propylamine (7)
Through a careful investigation to compare the reactivity
among primary O-alkyl thiocarbamate 1 and primary O-alkyl
carbamate 2, the C-N coupling reaction between O-propyl
thiocarbamate (1a) and O-propyl carbamate (2a) with
iodobenzene was examined. For this purpose, 1mmol of
iodobenzene was reacted with 1mmol of O-propyl
thiocarbamate (1a) and 1mmol of O-propyl carbamate (2a) in
the presence of the catalyst under the optimized conditions.
As it is depicted in scheme 2, analysis of the reaction mixture
disclosed appeared that O-propyl carbamate (2a) underwent
the C-N coupling more than O-propyl thiocarbamate (1a). This
could be due to the stronger nucleophilicity of the nitrogen
atom in O-alkyl carbamate 2 in comparison to O-alkyl
thiocarbamate 1, which is important in Cu catalyzed C-N
coupling reactions.
In the next step, a set of two reactions were designed to
confirm selectivity of the present method toward mono
N-arylation of primary O-alkyl thiocarbamate 1. For this
purpose, 1 mmol of O-propyl thiocarbamate (1a) was reacted
with 2 mmol iodobenzene under the optimized reaction
conditions. It was observed that in spite of using the excess
amount of iodobenzene, only mono N-arylation took place and
the product of N, N-diarylation was not detected in the
reaction mixture by TLC monitoring. In the second experiment,
1 mmol of O-propyl phenylthiocarbamate (4a) was treated
with 1 mmol of iodobenzene under the optimized reaction
condition. As shown in scheme 6, this reaction was not
preceded at all and O-propyl phenylthiocarbamate (4a)
remained intact. This might be due to stronger nitrogen
nucleophilicity and the less steric hindrance in O-propyl
thiocarbamate (1a) than O-propyl phenylthiocarbamate (4a).
Scheme 3. Reactivity of O-propyl thiocarbamate (1a) and
O-propyl carbamate (2a) toward N-arylation reaction.
In order to compare the reactivity among O-alkyl
thiocarbamates 1, thioamides and aliphatic amines toward the
C-N coupling reaction, the reaction of O-propyl thiocarbamate
(1a), butyrthioamide (6) and propylamine (7) with
iodobenzene in the presence of the catalyst under optimized
condition was chosen as a model reaction. Therefore, initially,
equimolar of O-propyl thiocarbamate (1a) (1mmol) and
Scheme 6. Study of selective mono N-arylation of O-propyl
thiocarbamate
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The magnetic property of the catalyst is demonstrated in responsible species that catalyzes the N-arylatioVniewreAarticctleioOnnlinise
Figure 2. According to this scheme, the catalyst has good the magnetic heterogeneous Cu (II) complex.
DOI: 10.1039/C9NJ00028C
dispersity in the reaction media and it can be easily removed
from the mixture by an external magnetic field.
Figure 4 represents the XRD pattern and FE-SEM image of
the recycled catalyst after the sixth run. This figure shows that
characteristic peaks of Fe3O4 are present. Also, Comparison of
the FE-SEM images between the fresh catalyst and recovered
catalyst after the sixth run demonstrates that Cu nanocatalyst
keeps its spherical shape with little agglomeration, which
might be the another important cause of yield decreasing.
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Figure 2. Photo images of magnetic field-responsive of the
Fe3O4@SiO2/Schiff base of Cu (II) nanoparticles before
magnetic field (A) and under magnetic field (B)
To determine the recyclability of the catalyst, after
completion of C-N coupling of O-propyl thiocarbamates (1a)
and phenyl iodide, the catalyst was removed from the mixture
by an external magnetic field because of the magnetic
property of the catalyst, which its magnetic field responsivity
has exhibited in Figure 3, and reused in another same reaction.
This process was repeated again and as it is depicted in Figure
4, the catalyst remains its catalytic activity over five runs. This
result is an evidence for the stability and efficiency of the
catalyst.
Figure 4. (a) XRD patterns of the recovered catalyst after the
sixth run; (b) and (c) TEM images of the catalyst before
reaction and after six cycles of reactions.
Inductively Coupled Plasma (ICP) analysis was also
performed for the fresh catalyst and the catalyst after first and
the sixth runs to determine the amount of copper leaching.
According to this test, the amount of copper on the fresh
catalyst was measured to be 0.21 mmol/g. ICP analysis showed
only 0.2% and 3.2 % copper leaching after the first and the
sixth runs respectively. These data along with the results
retrieved from the hot filtration test confirm the high
heterogeneity and stability of the catalyst.
Furthermore, for determine the stability of catalyst under
the reaction conditions, the recovered catalyst of model
reaction was weighed. After the first and the sixth runs,
respectively 0.0248 gr and 0.0245 gr of catalyst was recycled
that these results indicate the high stability and also the high
recovered ability of the catalyst with using an external
magnetic field.
Figure 3. Reuse of the catalyst for C-N coupling of O-propyl
thiocarbamate (1a) and iodobenzene.
Moreover, to determine responsible Cu species for carrying
out N-arylation of thiocarbamates, the hot filtration test was
performed. When the reaction time reached half done, the
catalyst nanoparticles were taken out from the reaction
mixture by an external magnetic field, the residue was allowed
to stir under the reaction conditions. The analysis of the
reaction mixture by TLC monitoring did not show any
considerable progress. These results showed that only a few
species of Cu may exist in the solution phase and the main
The active form of copper is generally believed to be Cu(I)
in C–N cross-coupling reactions. Copper catalysts in 0, +1, and
+2 oxidation states can be used to catalyze N-arylation
reactions. However, when Cu(0) or Cu(II) sources are used; the
active Cu(I) species is formed by in situ reduction or oxidation
of the copper source. In kinetic studies of the Ullmann
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coupling of phenyl halides with diphenylamine, Cu(I) halides
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Conclusions
View Article Online
In summary, we have described aDnOIe: f1f0i.c1i0e3n9t/,C9mNJil0d00a2n8Cd
selective mono N-arylation of primary O-alkyl thiocarbamates
1 and primary O-alkyl carbamates 2 derivatives with aryl
halides or arylboronic acids 3 in the presence of magnetic
copper (II) nanocatalyst. The method is tolerant of a variety of
functional groups in both primary O-alkyl thiocarbamates 1 or
carbamates 2 coupling partners allowing for further synthetic
manipulation. This recyclable catalyst offers advantages like
simple work-up and high yields. In addition, exploitation of this
work in the preparation of arrays of drug-like molecules is
currently underway.
give reaction rates that are significantly higher than when
Cu(II) salts are used.36 When Cu(II) precursors are used,
reduction to Cu(I) by alkoxide or amide reagents is observed.36,
37
Reduction of Cu(II) can be accelerated by ligands that
stabilize the Cu(I) oxidation state, such as neocuproine.38
Reduction of Cu(II) ions by amide or alkoxide ligands has been
confirmed by electron paramagnetic resonance (EPR)
spectroscopy of catalyst systems.39, 40 Amino acid complexes of
Cu(I) ions are observed under catalytic conditions by
electrospray–mass spectrometry (ESI–MS) analysis of reaction
mixtures.41
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According to the literature reports on the reduction of
Cu(II) to Cu(I) by alkoxide and amide reagents36, 37, 39, 40 and
acceleration this process by ligands that are able to stabilize
Experimental
General experimental:
41
the Cu(I) oxidation state,38,
the following plausible
mechanism might be proposed for N-arylation of primary
O-alkyl thiocarbamates and primary alkyl carbamates (Scheme
7). Initially, the copper (II) complex reduction is initiated by
t-butyl oxide or/and the primary thiocarbamate or the primary
carbamate, and then copper (I) complex is converted to copper
(III) intermediate I by oxidative addition of the aryl halide.
Finally, substitution of halide on the intermediate I by the
nucleophile (thiocarbamates or carbamates) produces III and
regenerates the active Cu (I) catalyst after occurring reductive
elimination reaction on the intermediate II.
Chemicals were purchased from the Merck, Flucka and
Aldrich Chemical Companies in high purity. The Cu(II) complex
supported on superparamagnetic Fe3O4@SiO2 nanoparticles,
primary O-alkyl thiocarbamates42 and primary O-alkyl
35a
carbamates43 skeletons were accessed following literature
protocols. The products were characterized by comparison of
their spectral and physical data such as NMR, FT-IR, CHNS and
melting point with available literature data. 1H and 13C NMR
spectra were recorded with Bruker Avance DPX 250MHz
instruments with Me4Si or solvent resonance as the internal
1
standard. H NMR spectroscopic data are reported as follows:
chemical shift, multiplicity (s = singlet, d = doublet, t = triplet,
q= quartet, quint = quintet, sext = sextet, sept = septet, br. =
broad, m = multiplet), coupling constants (Hz), and integration.
Fourier transform infrared (FTIR) spectra were obtained using
a Shimadzu FT-IR 8300 spectrophotometer. The hydrodynamic
size of the particles was measured by dynamic light scattering
(DLS) techniques, using a HORIBA-LB550 particle size analyzer.
Cu loading and leaching test were carried out with an
Inductively Coupled Plasma (ICP) analyzer (Varian, vista-pro).
Determination of the purity of the substrate and monitoring of
the
reactions
were
accomplished
by
thin-layer
chromatography (TLC) on a silica-gel polygram SILG/UV 254
plates.
35a
General procedure for the preparation of Fe3O4 nanoparticles:
To the solution of FeCl3∙6H2O (4.8 mmol) in deionized water
(15 mL), added a mixture of polyvinyl alcohol (PVA 15000) (1.0
g), as the surfactant, and FeCl2∙4H2O (4.5 mmol) in deionized
water (15 mL). The resultant solution was stirred for 30 min at
o
80 C. In the next step, hexamethylenetetramine (HMTA) (1.0
mol/L) was added dropwise with vigorous stirring to reach pH
o
10 and the resultant mixture was heated for 2 hours at 60 C.
The black magnetite solid produced was separated by an
external magnet and washed with hot ethanol three times and
Scheme 7. The plausible mechanism for the copper-catalysed
N-arylation of primary O-alkyl thiocarbamates 1 and primary
O-alkyl carbamates 2
o
dried at 80 C for 10 hours.
General procedure for the preparation of Fe3O4@SiO2 core-shell:
35a
Initially, in the first step, Fe3O4 (0.5 g, 2.1 mmol) was
dispersed in a solution of ethanol (50 mL), deionized water (5.0
mL) and tetraethoxysilane (TEOS) (0.2 mL). Then 5.0 mL of
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NaOH (10 wt%) was added and this mixture was left to be Na2SO4. Then the solvent was removed undVieewr Arrtieclde uOcnleinde
stirred for 30 min at room temperature. The pressure. The resulting crude product was purified by flash
superparamagnetic core shall (Fe3O4@SiO2) was separated by chromatography to give the desired cross-coupling products in
DOI: 10.1039/C9NJ00028C
an external magnet, washed with a solution of deionized water good to excellent isolated yields.
o
and hot ethanol three times and dried at 80 C for 10 hours.
General procedure for the synthesis of primary O-alkyl
35a
43
General procedure for preparation of the ligand:
A solution of carbamates: According to our reported procedure,
to a
the stoichiometric amount of salicylaldehyde (1.0 mmol, 0.122 mixture of alcohol (1.0 mmol) and potassium cyanate (1.5
g) in dry ethanol (25 mL) was added dropwise to the mmol) in a mortar, DBSA (1.5 mmol) was added and the
3-aminopropyl (triethoxy) silane (1.0 mmol, 0.176 g) in 25 mL mixture was pulverized until a uniform mixture was formed.
dry ethanol then the mixture was stirred at room temperature Then the mixture was kept in an oven at 60 OC for 1 hour.
for 6 hours. The resulting salen ligand, as the bright yellow After completion of the reaction, CH2Cl2 (15 mL) and the
precipitate, was separated by filtration and washed with hot saturated aqueous solution of NaHCO3 (15 mL) were added to
dry ethanol (5.0 mL) and then dried in vacuum. The crude the resulting powder and organic layer was extracted, washed
product was recrystallized from dry ethanol to obtain the pure with water (3×15 mL), dried over anhydrous Na2SO4 and
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product in 98% yield (0.271 g).
General procedure for preparation of the Cu(II) complex:
concentrated under vacuum to afford the title crude products.
Finally, the pure products were obtained by recrystallization
35a
Anhydrous Cu(OAc)2 (0.186 g, 1.0 mmol) was added to the from diethyl ether in high yields.
solution of the synthesized ligand (0.651 g, 2.0 mmol) in General procedure for the selective mono N-arylation of primary
ethanol (25 mL) and then the mixture was allowed to be O-alkyl carbamates 5: The catalyst (0.025 g, 0.5 mol %) was
refluxed for 12 hr. After the completion of complex formation, added to a mixture of primary O-alkyl carbamates (1.0 mmol),
which is determined by TLC monitoring, the resulting product, aryl halide (1.0 mmol) and sodium tert-butoxide (1.5 mmol) in
o
as a green colour precipitate, was filtered and washed with toluene. The mixture was mixed by heater stirrer at 100 C for
ethanol. Then the Cu(II) complex was purified by the appropriate time. The progress of the reaction was
recrystallization from ethanol in 95 yields (0.689 gr).
monitored by TLC. After completion of the reaction and
General procedure for preparation of the Cu(II) complex separation of the catalyst by a magnetic field, 20 ml H2O was
35a
supported on superparamagnetic Fe3O4@SiO2 nanoparticles:
added and the mixture was extracted with CHCl3. The organic
Fe3O4@SiO2 (2.0 g) was added to the solution of Cu(II) complex phase was washed with water (2 × 10 mL) and dried over
(1.0 mmol) in ethanol (10 mL) and the resultant mixture was anhydrous Na2SO4. Then the solvent was removed under
refluxed for 12 hours. Then, the produced superparamagnetic reduced pressure. The resulting crude product was purified by
nanoparticles (Fe3O4@SiO2/Cu(II) complex), was separated by flash chromatography to give the desired cross-coupling
o
an external magnet and dried at 80 C overnight. The product products in good to excellent isolated yields.
was washed with hot ethanol and water to remove unreacted
species and dried at 80 oC for 6 h.
Acknowledgments
Authors gratefully acknowledge the financial support of this
work by the research council of Shiraz University.
General procedure for the synthesis of primary O-alkyl
thiocarbamates: According to our reported procedure,:42 DBSA
(1.5 mmol, 0.489 g) was added to a mixture of potassium
thiocyanate (1.0 mmol, 0.097) and alcohol or phenol (1.0
o
mmol). Then, the mixture was heated and stirred at 60 C in an
oil bath for 12 h. The reaction was monitored by TLC. After
completion of the reaction, CH2Cl2 (10 mL), and saturated
NaHCO3 (10 mL) were added. The organic layer was separated
from the aqueous layer and washed twice with water
(2×10mL). The organic layer was concentrated under reduced
pressure and the crude product was purified on a column of
silica gel by a mixture of petroleum ether and ethyl acetate
(9:1) as the solvent, to provide the desired pure products in
high yields.
General procedure for the selective mono N-arylation of primary
O-alkyl thiocarbamates: The catalyst (0.025 g, 0.5 mol%) was
poured in a mixture of primary O-thiocarbamates (1.0 mmol),
aryl halide (1.0 mmol) and sodium tert-butoxide (1.5 mmol) in
toluene. The mixture was stirred at 100 °C for the appropriate
time. The progress of the reaction was monitored by TLC. After
completion of the reaction (Monitored by TLC) and separation
of the catalyst by a magnetic field, 20 mL of H2O was added
and the mixture was extracted with CHCl3. The organic phase
was washed with water (2 × 10 mL) and dried over anhydrous
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DOI: 10.1039/C9NJ00028C
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A convenient and efficient selective mono N-arylation of primary O-alkyl thiocarbamates and
carbamates is reported by recyclable magnetic Cu(II) nanocatalyst.