Three-component synthesis of N-sulfonylformamidines in the presence of magnetic cellulose supported N-heterocyclic carbene-copper complex, as an efficient heterogeneous nanocatalyst

Article abstract of DOI:10.1016/j.tetlet.2017.08.075

A cellulose based magnetic nanocomposite possessing NHC-Cu Complex has been synthesized and characterized. It was then applied as a highly active catalyst in one-pot three-component reaction of sulfonyl azides, secondary amines and triethylamine to afford

Full text of DOI:10.1016/j.tetlet.2017.08.075

Accepted Manuscript
Three-component synthesis of N-sulfonylformamidines in the presence of mag-
netic cellulose supported N-heterocyclic carbene-copper complex, as an effi-
cient heterogeneous nanocatalyst
Salman Shojaei, Zarrin Ghasemi, Aziz Shahrisa
PII:
S0040-4039(17)31097-3
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.08.075
TETL 49265
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
25 June 2017
27 August 2017
29 August 2017
Please cite this article as: Shojaei, S., Ghasemi, Z., Shahrisa, A., Three-component synthesis of N-
sulfonylformamidines in the presence of magnetic cellulose supported N-heterocyclic carbene-copper complex, as
an efficient heterogeneous nanocatalyst, Tetrahedron Letters (2017), doi: http://dx.doi.org/10.1016/j.tetlet.
2017.08.075
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Three-component synthesis of N-sulfonylformamidines in the presence of magnetic cellulose
supported N-heterocyclic carbene-copper complex, as an efficient heterogeneous nanocatalyst
Salman Shojaei, Zarrin Ghasemi* and Aziz Shahrisa*

1
Tetrahedron Letters
journal homepage: www.els evier.com
Three-component synthesis of N-sulfonylformamidines in the presence of
magnetic cellulose supported N-heterocyclic carbene-copper complex, as an
efficient heterogeneous nanocatalyst
Salman Shojaei, Zarrin Ghasemi* and Aziz Shahrisa*
Department of Organic and Biochemistry, Faculty of Chemistry, University of Tabriz, Tabriz 5166614766, Iran. E-mail: z.ghasemi@tabrizu.ac.ir; Fax:
+984133340191
ARTICLE INFO
ABSTRACT
Article history:
Received
A cellulose based magnetic nanocomposite possessing NHC-Cu Complex has been synthesized
and characterized. It was then applied as a highly active catalyst in one-pot three-component
reaction of sulfonyl azides, secondary amines and triethylamine to afford N-
sulfonylformamidines. Copper catalyzed oxidative transformation of C-N bond of triethylamine
is a key step to give desired products. In contrast with the good reactivity of the conventional
secondary amines, aromatic amines and NH containing heteroaromatics had no activity in these
reactions. Moreover, the used nanocatalyst which could be recovered by external magnet,
showed reasonable catalytic activity for several times.
Received in revised form
Accepted
Available online
Keywords:
Cellulose
Magnetic nanocomposite
N-sulfonylformamidines
Copper catalyzed reactions
Nanocatalyst
Introduction
with sulfonyl azides, sulfonamides, sodium sulfinate salts or
sulfonyl chlorides16 and (f) the coupling of amines and sulfonyl
hydrazides. 17
Construction of high prevalence of valuable nitrogen-
containing organic compounds via appropriate methods is highly
required due to modern health and environmental concerns. The
transformation of C-N bonds catalyzed by transition metal
complexes is a fascinating methodology for these criteria.1, 2 The
process of making proteins from ꢀ-amino acids and the reverse
process from proteins to ꢀ- amino acids via the formation and
cleavage of C-N bond in the presence of enzymes could be well
fitted example in this field.3
Sulfonyl containing moieties (sulfonylamidines and
sulfonamides) as well-known structural motifs are privileged
class of functional groups in pharmaceuticals, bioactive and
natural products.4-7 They have been found as an integral part of
various drugs or drug-like molecules due to their structurally
rigid, hydrogen bonding capabilities and potential role as non-
cleavable amide surrogates.8 Additionally, they have been
successfully implemented
a broad spectrum of biological
activities such as inhibitors of anthrax lethal factors,
antagonists/inverse agonists, antiproliferative, antiresorptive,
antitumor and anticancer agents (Figure 1).6, 9, 10 The emergence
of sulfonylamidines as bioactive pharmacophores has led to
numerous new synthetic developments to embed this highly polar
moieties onto organic molecules.11 In this context efficient
approaches have been developed to achieve these goals. These
include (a) condensation of sulfonamides with formamide,12 (b)
three-component coupling of sulfonamides or sulfoximines with
terminal alkynes and amines,13 (c) the coupling of primary,
secondary or tertiary amines with sulfonyl azides and terminal
alkynes,14 (d) coupling of thioamides and sulfonyl azides,15 (e)
oxidative C-N bond cleavage by the reaction of tertiary amines
Fig. 1. Some pharmaceuticals based on sulfonylamidines.
In recent years, N heterocyclic carbenes (NHCs) as versatile
class of ancillary ligands have been extensively studied in
organometallic synthesis, catalysis and many useful organic
transformations such as C-C, C-N and C-O bond formations.18-21
The stronger interaction between the metal and these ligands
compared to phosphine ligands, is due to be strong ꢁ donors,
weak ꢂ acceptors and some steric and electronic properties.
Furthermore, increased stability towards air and moisture, have
resulted in a wide range of catalytic applications for NHC
complexes.22 However some basic problems such as separation

2
Tetrahedron Letters
and recycling, reveals the necessity of donating a heterogeneous
dispersive X ray spectroscopy (EDX) mapping. Figure 3 shows
the homogeneous distribution of copper elements which have
been uniformly dispersed on the whole surface of the NHC-
Cu@MCs nanocomposite.
nature as well as superparamagneticity to the NHC catalyst.23
Biopolymers, such as cellulose have been used as renewable
bioresources in catalytic technology and medicinal applications.24
Thereby, we have focused our attention on modified cellulose as
The EDX (Energy-Dispersive X-ray) analysis of NHC-
Cu@MCs nanocatalyst was also studied (Figure 4). The
nanocatalyst comprises C, O, N, Cu, I and Fe elements that
demonstrate the coated CuI and Fe3O4 on the nanocatalyst
structure.
proper support for copper catalysts in the synthesis of N-
sulfonylamidines.25,
26
Their non toxicity, bio degradability,
high surface area, good mechanical stability and adsorption
capacity, convinced us to construct this type of the nanocatalyst
for the synthesis of N-sulfonylformamidines. Herein we report a
new effective strategy based on cellulose incorporated NHC-Cu
complex in the oxidative three-component reactions of
sulfonylazides, secondary amines and triethylamine to afford the
desired amidines for first time. Copper mediated transformations
of carbon-nitrogen bond of triethylamine which run the formation
of active intermediates in the presence of oxygen, are then
discussed.
Results and discussion
We have reported the synthesis of a magnetic nanocatalyst
based on ionic liquid grafted cellulose (IL-g-MCs) and the using
of it for synthesis of N-solfunylamidines.25 Addition of this
nanocomposite to a suspension of copper(I) iodide and sodium
tert butoxide in THF with vigorous stirring for 8 h at 60°C,
afforded the corresponding N heterocyclic carbene (NHC-
Cu@MCs) (Scheme 1). The loaded percentages of Cu and Fe
ions in the nanocatalyst were determined by flame atomic
absorption spectroscopy (FAAS), to be 7.86 and 26.67 w/w%
respectively. The catalyst was also characterized using TGA,
XRD, SEM, EDX, VSM and FT IR instrumental techniques.
Thermogravimetric analysis (TGA) was considered to evaluate
the thermal stability of the NHC-Cu@MCs. The thermogram
displayed an initial weight loss of 2.23% ascribed to desorption
of physically adsorbed water below 100°C. The second weight
loss of 43.43% up to 270-350 °C is attributed to decomposition
of NHC-Cu complex and cellulosic part of nanocomposite
(Figure 2). This observation indicates that the synthesized
nanocatalyst is stable up to 270 °C.
Fig. 2. TGA thermogram of NHC-Cu@MCs in air.
For investigating the surface morphology and size of
nanoparticles, the scanning electron microscopy (SEM) analysis
of NHC-Cu@MCs was done (Figure 3). The resulting images
show uniform and minuscule CuI and Fe3O4 particles which
approximate average size is determined to be about 30-50 nm.
The density and distribution of the NHC Cu group on the
synthesized nanocomposite were also evaluated by energy
Fig. 3. SEM images of NHC-Cu@MCs: (a) 20 ꢃm; (b) 1 ꢃm; (c) 500 nm
and (d) EDX elemental mapping of Cu.
Scheme 1. Synthesis of cellulose based magnetic nanocomposite immobilized NHC-Cu complex (NHC-Cu@MCs).

3
Fig. 4. EDX pattern of NHC-Cu@MCs.
The X-ray diffraction (XRD) was used to investigate the
crystalline structure of NHC-Cu@MCs nanocatalyst (Figure
5). The peaks at (2ꢄ = 30.29°, 35.62°, 43.08°, 54.16°, 57.39°
and 62.72°) for iron oxide and the peaks at (2ꢄ = 25.55°,
29.39°, 31.46°, 34.00°, 42.32°, 52.95°, 62.00°, 66.84° and
68.72°) for copper are related to the characteristic peaks of
the nanocatalyst. The size of the nanoparticles was estimated
using the Debye-Scherrer formula to be 15 nm at 2θ = 35.62°
(main peak) for iron oxide and 30 nm at 2θ = 34.00° (main
peak) for copper.
Fig. 6. FT IR spectra for cellulose (I), ionic liquid grafted magnetic
cellulose (II) and nanocatalyst (NHC-Cu@MCs) (III).
Fig. 7. Magnetization curve of NHC-Cu@MCs.
The catalytic efficiency of synthesized nanocomposite,
NHC-Cu@MCs, was then explored in multicomponent
reaction of secondary amines, sulfonyl azides and
triethylamine for the synthesis of N-sulfonylformamidines.
To optimize the reaction conditions, tosylazide (1 mmol),
morpholine (1 mmol) and triethylamine (1.2 mmol) were
treated in the presence of various amounts of synthesized
nanocatalyst in different solvents at room temperature (Table
1, entries 1-12). The best results were obtained by using of
20 mg (2.4 mol% of Cu) of catalyst in solvents such as
tetrahydrofuran (THF) or acetonitrile (CH3CN) (entries 2, 5).
Increasing the amount of catalyst to 25 and 30 mg, did not
improve the yield of product (entries 3, 4). Examining the
other copper based catalysts in this reaction (entries 14-19),
appeared the more efficiency of copper (I) iodide (entry 14).
It should be noted that, when the reaction was tested in the
absence of catalyst or solvent free conditions, the
sulfonamide products were obtained by only participation of
morpholine and tosylazide, instead of sulfonylformamidine
product (entries 13, 20).
Fig. 5. XRD pattern of NHC-Cu@MCs nanocatalyst.
The nanocatalyst was also characterized using Fourier
transform infrared (FT IR) spectroscopy. As Figure 6
shows, in the spectrum of nanocatalyst, NHC-Cu@MCs,
(III), peaks at 1643 and 1451 cm−1 are due to the stretching
vibrations of CꢅN and CꢅC in the imidazolium rings of
functionalized polymer, respectively.25, 28, 29 The band at 594
cm−1 can be assigned to the vibration of Fe-O bond in Fe3O4.
The expected characteristic peak at 670 cm−1 which could be
attributed to copper iodide, is not visible due to the
overlapping bands around 600–700 cm-1. 30, 31
The magnetic property of the synthesized nanocatalyst
was measured using vibrating sample magnetometry. Figure
7 shows the magnetization curve as a function of applied
magnetic field (Oe) in the range -10000 to 10000 Oe. Zero
remanence and coercivity of the magnetization curve
demonstrate that the synthesized nanocatalyst has
superparamagnetic properties and could be separated from a
reaction mixture, leading to easy recycling and reuse.

4
Tetrahedron Letters
Table 1 Optimization of the reaction conditions.
Entry
Catalyst (mg, mol %)
NHC-Cu@MCs (10 mg)
NHC-Cu@MCs (20 mg, 2.4 mol %)
NHC-Cu@MCs (25 mg)
NHC-Cu@MCs (30 mg)
NHC-Cu@MCs (20 mg)
NHC-Cu@MCs (20 mg)
NHC-Cu@MCs (20 mg)
NHC-Cu@MCs (20 mg)
NHC-Cu@MCs (20 mg)
NHC-Cu@MCs (20 mg)
NHC-Cu@MCs (20 mg)
NHC-Cu@MCs (20 mg)
NHC-Cu@MCs (20 mg)
CuI (10 mol %)
Solvent
CH3CN
CH3CN
CH3CN
CH3CN
THF
Time (h)
Yielda (%)
1
2.5
2.5
2.5
2.5
2.5
4
83
88
88
86
87
65
70
76
43
-
2
3
4
5
6
CHCl3
CH2Cl2
1, 4-Dioxane
Toluene
H2O
7
4
8
4
9
4
10
4
11
EtOH
4
45
35
-
12
DMF
4
13
-
2.5
2.5
2.5
4
14
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
75
63
30
42
53
47
-
15
CuBr (10 mol %)
16
CuBr2 (10 mol %)
17
CuSO4 (10 mol %)
5
18
Cu (OAc)2 (10 mol %)
Cu (NO3)2.3H2O (10 mol %)
-
5
19
20
2.5
2.5
aIsolated yields.
The proposed mechanism for formation of the formamidine
product is postulated in Scheme 2. The reaction initiates with
coordination of triethylamine by copper catalyst to produce
ammonium intermediate I. Removal of acidic proton of the
methylene, resulted in the oxidative formation of C=N bond
to give ꢂ-coordinated iminium cation II in air. It should be
noticed that, stirring of the reactants under optimized
conditions at argon atmosphere (without air) showed no
progress of the reaction even at prolonged times.
Nucleophilic attack of secondary amine to iminium ion II,
leads to the complex III. Base mediated elimination reaction,
produces the tertiary vinyl amine IV which undergoes 1, 3-
dipolar cycloaddition reaction with sulfonyl azide to afford a
triazoline intermediate V. Cleavage of the unstable
intermediate V by release of one mole of CH2N2, gives the
desired formamidine product.
1-methylpiperazine (contains both secondary and tertiary
amine sites) and treated with tosylazide and triethylamine,
which led to unexpected sulfonamides 4m and 4n (entries
17, 18). Apparently, the existence of other tertiary amine, has
prevented coordination of triethylamine to copper catalyst
and formation of formamidine product. It should be
emphasized that the reaction of 1-methylpiperazine with
sulfonylazide results in the corresponding sulfonamide only
in the presence of a base such as K2CO3 or Et3N.32 Thus the
role of triethylamine as base in the formation of products 4m
and 4n is proved. Primary amines such as butylamine and
aniline and also aromatics such as imidazole and pyrazole
were inactive in these reactions (Table 2, entries 19 23).
Moreover, it could be expected that according to the
26
structure of our previous reported compounds,25, all the
products have E configuration. This selectivity can be
confirmed by 1H NMR spectra, which demonstrate no
isomeric protons. It is important to mention that when N-
methylcyclohexylamine was selected as substrates, although
We then probed the general applicability of this protocol
by treatment of sulfonylazides, triethylamine and secondary
amines 3a-j (Table 2). The results showed excellent
tolerance for diverse derivatives of N-sulfonylformamidines
4a-l (entries 1-12). It is worth noting that, in the cases of
1
the TLC of reaction mixture showed a single product, its H
NMR and 13C NMR spectra indicated the formation of two
isomeric products. These are probably due to the existence of
two diastereomeric forms of N-sulfonylformamidine product
(axial and equatorial forms, Scheme 4). In all two products
(4g and 4h), the equatorial forms were predominant (Table 2,
sterically
hindered
secondary
amines
such
as
diisopropylamine (3h) and dicyclohexylamine (3i), the
products 4i and 4j were obtained instead of expected
sulfonylformamidines (entries 13-16), which shows that
amines 3h and 3i are inactive in these reactions. It should be
noticed that the treatment of sulfonylazides with
triethylamine in the presence of the copper catalyst also
afforded to products 4i or 4j. Therefore it seems most likely
the enamine tautomer III which can be formed by the
hydrogen abstraction from iminium ion II by triethylamine,
runs the 1,3-cycloaddition reaction with sulfonylazide to
give the products 4i and 4j (Scheme 3). When we treated the
obtained N,N-diethyl-N'-tosyl-formamidine (4i) with
morpholine in the presence of the catalyst, we did not
observe the expected product 4a. This result also proves the
proposed mechanisms in schemes 2 and 3. We also selected
1
entries 7, 8). In their H NMR spectra, the notable difference
in chemical shifts of protons attached to cyclohexyl ring (Hα
and Hβ) indicates that one of these protons, Hα, is located in
the equatorial position (Axial form) and the other, Hβ, in the
axial situation. It shows that the cyclohexyl ring in these
structures is not rigid and the inversion is being appointed.25,
26

5
Scheme 3 Proposed mechanism of the reactions in the presence of
sterically hindered amines.
Scheme 2 Proposed mechanism for the formation of
sulfonylformamidines 4a-l.
N
Table 2 Synthesis of N-sulfonylformamidine derivatives 4a-l in the presence of NHC-Cu@MCs.a
Entry
1
R1
Amine
Time (min)
2.5
Product
Yieldb (%)
4-MeC6H4
88
3a
3a
4a
4b
4c
2
3
Ph
2.5
2.5
86
87
4-MeC6H4
3b
3b
4
5
6
Ph
4-MeC6H4
Ph
2.5
2.5
2.5
85
88
87
4d
4e
3c
3c
4f

6
Tetrahedron Letters
85c
7
4-MeC6H4
3
ax:eq
3d
3d
(18:82)
4g
83c
ax:eq
8
Ph
3
(18:82)
4h
9
4-MeC6H4
4
4
5
83
83
67
3e
3e
4i
10
11
Ph
4j
4-MeC6H4
3f
4k
O
O
S
N
N
Ph
12
13
4-MeC6H4
4-MeC6H4
3
5
81
76
Ph
3g
4l
4i
3h
3h
14
15
16
Ph
4-MeC6H4
Ph
5
5
5
4j
4i
4j
73
78
75
3i
3i
17
18
4-MeC6H4
1
1
94
92
4m
3j
3j
4-MeC6H4
4n
-
19
20
4-MeC6H4
4-MeC6H4
8
8
-
-
3k
3l
-

7
21
4-MeC6H4
8
-
-
3m
22
23
4-MeC6H4
4-MeC6H4
8
8
-
-
-
-
3n
3o
a Reaction conditions: Sulfonyl azide (1 mmol), Secondary amines (1mmol), triethylamine (1.2 mmol), NHC-Cu@MCs (20 mg),
CH3CN (3 mL), room temperature.
b Isolated yield.
c Ratio of minor/major products.
Scheme 4 Axial and equatorial forms of N methylcyclohexylamine derived sulfonylformamidine products 4g and 4h.
The recyclability of the NHC-Cu@MCs composite was also
studied using the model reaction. It was found that the
recovery can be achieved at least five reaction runs and
revealed a minimal loss in catalytic activity (Figure 8). After
each cycle, the used catalyst was recovered using an external
magnet, washed with acetone and ethanol, dried under
vacuum and used directly for the next cycle.
characterized by recyclability of the catalyst without any
marked change in catalytic activity.
Acknowledgment
We gratefully acknowledge financial support from the
Research Council of University of Tabriz.
Supplementary data
1
Spectra and characterization data (IR, H, and 13C NMR) of
compounds and experimental section associated with this
article can be found in the online version.
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9
ꢀ Oxidative three-component synthesis of N-
sulfonylformamidines
ꢀ Copper catalyzed oxidative transformation
of C-N bond
ꢀ Applying of biopolymer nanocatalyst, based
on N-heterocyclic carbene-copper complex