Solvent selective phenyl selenylation and phenyl tellurylation of aryl boronic acids catalyzed by Cu(II) grafted functionalized polystyrene

Article abstract of DOI:10.1016/j.tetlet.2014.12.055

A solvent-selective methodology for the phenyl selenylation and phenyl tellurylation of aryl boronic acids has been developed for the first time using a polymer supported Cu(II) catalyst. The catalyst was synthesized by anchoring Cu(OAc)₂ onto a functionalized polystyrene with pyridine thiosemicarbazone ligand. It was then characterized properly by SEM, EDAX, FT-IR, TGA, and EPR experiments. The catalyst smoothly catalyzes phenyl selenylation of aryl boronic acids in water and phenyl tellurylation of aryl boronic acids in PEG-600, selectively. Thus a wide variety of unsymmetrical organodiaryl or aryl-heteroaryl selenides and tellurides have been synthesized by this protocol. The catalyst was recycled up to six runs without any appreciable loss of catalytic activity.

Full text of DOI:10.1016/j.tetlet.2014.12.055

Accepted Manuscript
Solvent selective phenyl selenylation and phenyl tellurylation of aryl boronic
acids catalyzed by Cu(II) grafted functionalized polystyrene
Susmita Roy, Tanmay Chatterjee, Sk. Manirul Islam
PII:
S0040-4039(14)02121-2
DOI:
http://dx.doi.org/10.1016/j.tetlet.2014.12.055
TETL 45579
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
23 September 2014
4 December 2014
10 December 2014
Please cite this article as: Roy, S., Chatterjee, T., Manirul Islam, Sk., Solvent selective phenyl selenylation and
phenyl tellurylation of aryl boronic acids catalyzed by Cu(II) grafted functionalized polystyrene, Tetrahedron
Letters (2014), doi: http://dx.doi.org/10.1016/j.tetlet.2014.12.055
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Solvent selective phenyl selenylation and phenyl tellurylation of
aryl boronic acids catalyzed by Cu(II) grafted functionalized
polystyrene
Susmita Roya, Tanmay Chatterjee*b and Sk. Manirul Islam*a
aDepartment of Chemistry, University of Kalyani, Nadia, 741235, West Bengal, India.
bDepartment of Organic Chemistry, Indian Association for the Cultivation of Science,
Kolkata-700032, India.
Abstract
A solvent-selective methodology for the phenyl selenylation and phenyl tellurylation
of aryl boronic acids has been developed for the first time using a polymer supported Cu(II)
catalyst. The catalyst was synthesized by anchoring Cu(OAc)2 onto a functionalized
polystyrene with pyridine thiosemicarbazone ligand. It was then characterized properly by
SEM, EDAX, FT-IR, TGA, and EPR experiments. The catalyst smoothly catalyzes phenyl
selenylation of aryl boronic acids in water and phenyl tellurylation of aryl boronic acids in
PEG-600, selectively. Thus a wide variety of unsymmetrical organodiaryl or aryl- heteroaryl
selenides and tellurides has been synthesized by this protocol. The catalyst was recycled upto
six runs without any appreciable loss of catalytic activity.
Keywords: Phenyl selenylation and tellurylation, aryl boronic acids, solvent selective,
Cu@PS-TSC, recyclable.
*Authors to whom correspondence should be addressed.
Dr. Sk. Manirul Islam, Department of Chemistry, University of Kalyani, Kalyani, Nadia,
741235, W.B., India. Phone: +91-33-2582-8750, Fax: +91-33-2582-8282, e-mail:
manir65@rediffmail.com
bDepartment of Organic Chemistry, Indian Association for the Cultivation of Science,
Jadavpur, Kolkata 700032, India. E-mail: tanmay.chemistry@gmail.com
1

Organochalcogens, especially organoselenides and organotellurides are found as a
structural motifs in a wide variety of molecules of interest to biological, pharmaceuticals
and material sciences.1 They have also received considerable attention as synthetic
reagents or intermediates in organic synthesis.2 Thus, several methods have been explored
to synthesise organoselenide and organotelluride derivatives.3
The reaction of metal selenolate or tellurolate with various electrophiles like
organic halides, epoxides, acyl halides, -enones etc. was found to be the most
commonly used and general method to introduce the selenium or tellurium moiety into an
organic molecule.4 But the main challenge depends on the synthesis of organoselenides or
tellurides from aryl halides by using the common method because of the relatively lower
reactivity of aryl-halogen bond.
Though several methods have been developed using a transition-metal catalyst like
Pd,5 Ni,6and Cu7 for the synthesis of diaryl sulphides and selenides, but the synthesis of
diaryl tellurides is not so successful by these protocols. However, due to the instability and
toxicity of PhSeH or PhSeNa those methods are not desirable in the context of green
chemistry. To overcome this problem diarylchalcogenides which are relatively stable, less
toxic and easily available were employed.8 L. Wang9 et al. have first employed
organoboronic acids instead of aryl halide because of their stability, nontoxicity, easy
accessibility and compatibility with various functional groups.10 After that, the organic
boronic acid has become the reagent of choice for the reaction with diaryl
dichalcogenides.11 Several transition metal catalyzed synthesis of organoselenides and
tellurides were reported which include CuI,9,11a iron,11b InBr3,11cCuO-NPs,11d CuFe2O4-
NPs11e, 11f etc. However, most of those methodologies use homogeneous catalysts and
hazardous solvent like DMSO which are also not desirable in the context of green
chemistry.
Heterogeneous catalysis has gained considerable attention since last decade.12
With our continued interest on heterogeneous catalysis,13 we have developed a new
heterogeneous copper catalyst Cu@PS-TSC by immobilizing Cu(OAc)2 onto the surface
of a thiosemicarbazone functionalized polystyrene which was then applied to catalyze the
cross coupling reaction of aryl boronic acids with diphenyldiselenide or
diphenylditelluride. A solvent selective methodology for the phenyl selenylation and
tellurylation of aryl boronic acids has been carried out in water and PEG-600 respectively
to synthesize a library of organo mono selenides and tellurides (Scheme 1).
2

(PhTe)2,
(PhSe)2,
Cu@PS-TSC
(1.2 mol%)
Cu@PS-TSC
(1.2 mol%)
R Te Ph
R-B(OH)2
R Se Ph
K2CO3, PEG-600,
K2CO3, H2O,
70 oC, 8-10 h.
80 oC, 8-10 h, N2 atm
R = aryl or heteroaryl
Scheme 1. Solvent selective phenyl selenylation and tellurylation of aryl boronic acids.
The preparation of the catalyst Cu@PS-TSC is outlined below (scheme 2).
CH3
+ H2N
S
N
NH
MeOH
Reflux
S
N
N
NH
NH2
H2N
O
CH3
3
1
2
N
MeOH
+
P
3
NH
C
Cl
NH
N
P
S
C
CH3
4
N
Cu(OAc)2
NH
C
CH3COOH
NH
S
N
C
P
CH3
Cu
OAc
AcO
5
Cu@PS-TSC
Scheme 2. Synthesis of Cu@PS-TSC catalyst
At first, the 4-acetylpyridine thiosemicarbazone ligand was synthesized according to a
reported procedure.14 A mixture of 4-actetylpyridine 1 (0.10 mol) and thiosemicarbazone 2
(0.10 mol) was refluxed in methanol (100 mL) for 2h. After cooling at room temperature, a
white solid was precipitated out. The precipitate was then separated out from the reaction
mixture by simple filtration. It was washed with methanol and then recrystallized from warm
methanol to furnish pure 4-acetylpyridine thiosemicarbazone ligand 3. In the next step, the
chloromethylated polystyrene (2 g) was added to a methanolic solution of 4-acetylpyridine
thiosemicarbazone ligand 3 (1.07 gm in 20 mL). Then it was refluxed for 20 h at 60 0C. After
3

cooling at room temperature, yellow polystyrene beads were separated out from the reaction
mixture which was then washed thoroughly with methanol followed by drying under vacuum.
After that, polystyrene-anchored ligand 4 (2 g) was added to acetic acid (20 mL). Copper
acetate (0.05 g) in acetic acid (5 mL) was added to the above suspension with constant
stirring and then the solution was refluxed for 24 h. After cooling the reaction mixture to
room temperature, the separated greenish yellow solid 5 was filtered out, washed thoroughly
with methanol and dried under vacuum.
Due to the insolubility of the functionalized polystyrene and Cu@PS-TSC catalyst in
all common solvents, their structural investigations were limited only to their physico-
chemical properties like SEM, TGA-DTA, IR, and EPR analyses. The copper content was
determined by Varian, USA, and AA240 atomic absorption spectrophotometer (AAS).
Amount of metal was determined by stripping the bound metal from the support and analysis
by using atomic absorption spectrophotometer. Copper content was found in the catalyst is
2.27 wt% of Cu analyzed by AAS. Copper content was remained almost unchanged even
after recycling the catalyst for six cycles.The morphology of the catalyst was studied using
Scanning Electron Microscope (SEM). The micrographs of the polymer-anchored ligand and
Cu@PS-TSC catalyst were obtained from the scanning electron microscope and are presented
in figures 1a and 1b respectively. The pure chloromethylated polystyrene beads have smooth
surface (not shown). Incorporation of the ligand onto the polystyrene beads introduces a
slight roughness on its top layer (Figure. 1a). This roughness is relatively more prominent in
the metal complex (Figure 1b) which may be due to the loading of copper metal on polymer
anchored ligand.
(a)
(b)
Figure 1. FESEM image of (a) ligand 4 and (b) Cu@PS-TSC5
The polymer anchored ligand exhibits a broad band around 3300-3450 cm-1 due to –NH
stretching (secondary amine) vibrations. It also shows peaks at 1155 and 1641 cm-1 due to
4

C=S) and C=N) groups. These peaks shifted to lower frequency in the polymer anchored
metal complex due to the coordination of metal centre with the ligand. This suggests that the
ligand acts as a bidentate chelating agent coordinated through ‘N’ (azomethine) and ‘S’
atom.15 The pyridine ring vibrations were assigned at 1605, 1571, 1452 and 771 cm-1. These
bands are also present in the Cu@PS-TSC complex which means pyridine ring does not
participated in the complexation. A medium intensity band observed at 1363 cm-1 which
suggests the monodentate coordination of the acetate group.
Thermal stability of the complex was investigated using Thermo Gravimetric
Analysis (TGA). The polymer anchored ligand is stable in the temperature range 370-380 oC
o
and polymer anchored copper catalyst is stable upto 400 C. It indicates that after
complexation with metal the thermal stability of polystyrene increases by 30 oC.
The EPR (electron paramagnetic resonance) spectra of the fresh and used Cu@PS-
TSC catalyst were recorded for the solid sample at room temperature by a JES-FA200 ESR
spectrometer (JEOL) (Figure. 2). The X-band EPR spectrum of the fresh and used catalyst
show four hyperfine lines resulting from the coupling of the unpaired electron with the
nuclear spin of copper(II). In the EPR spectra of fresh catalyst (Figure. 2a), the signal of
Cu(II) is centred at g = 2.17 while in the EPR spectra of the used catalyst (Figure. 2a) the
signal of Cu(II) is centred at g = 2.11. It is also clear from the spectra of the used catalyst
that a slight rhombic distortion took place at the metal centre in the used catalyst.
Figure 2.EPR spectra of (a) fresh Cu@PS-TSC and (b) used Cu@PS-TSC.
To optimize the reaction conditions, a series of experiments were carried out with the
variation of several parameters like base, solvent, temperature and time for a representative
5

reaction of 4-methoxy phenyl boronic acid and diphenyldiselenide in presence of Cu@PS-
TSC (1.2 mol% of Cu) catalyst. The results are tabulated in Table 1.
Table 1.Optimization of reaction conditionsa for selenylation of aryl boronic acid
Cu@PS-TSC
(1.2 mol% of Cu)
Base, Solvent
Temp.(oC), Time (h)
Se
B(OH)2
Ph2Se2
+
MeO
MeO
Time (h) Yieldb (%)
Base
Temp (oC)
Solvent
Entry
1
2
3
DMF
100
10
10
10
92
82
88
-
Cs2CO3
100
K2CO3
K2CO3
K2CO3
DMF
DMSO
THF
100
100
100
80
4
5
6
7
8
10
10
K2CO3
K2CO3
K2CO3
K2CO3
H2O
H2O
H2O
H2O
92
10
10
8
92
92
92
70
70
80
9
K2CO3
K2CO3
H2O
H2O
60
70
8
6
10
11c
78
61
H2O
K2CO3
70
8
a Reaction conditions : 4-methoxy phenylboronic acid (1 mmol),
diphenyldiselenide(0.5 mmol), K2CO3 (1.5 mmol), Cu@PS-TSC
(1.2 mol% of Cu), H2O(4 ml).
b yields refer to those of isolater pure products.
c 0.8 mol % of Cu catalyst was used.
Though both Cs2CO3 and K2CO3 produced similar results in DMF solvent (Table 1,
entry 1 and 2), K2CO3 has been chosen as the base due to its relative mildness and low cost
than Cs2CO3. Among various solvent like DMF, DMSO, H2O and THF, water was found to
be the best solvent. Hence, the best result in terms of yield and time was achieved in water at
o
70 C in the presence of K2CO3 (1.5 equiv.) for 8 h (Table 1, entry 8). It was also observed
that with the decrease of catalyst loading (0.8 mol% of Cu), corresponding yield of the
product also decreases (Table 1, entry 11).
Interestingly, under the similar reaction conditions when 4-methoxy phenyl boronic
acid was subjected to react with diphenyl ditelluride, it produced only 25% yield of the
corresponding product (Table 2, entry 1). To optimize the reaction conditions for phenyl
tellurylation of 4-methoxy phenyl boronic acid several reactions were carried out with the
variation of solvent, temperature and time. The results are summarised in Table 2.Though the
reaction in DMF and DMSO solvent produced good yields (Table 2, entry 2, 3), PEG-600
6

was found to be the best solvent for the phenyl tellurylation of 4-methoxy phenyl boronic
acid in terms of yield and time at 80 oC (Table 2, entry 9).
Table 2. Optimization of reaction conditions for tellurylation of aryl boronic acidsa
Cu@PS-TSC
(1.2 mol% of Cu)
B(OH)2
+
Te
Ph2Te2
K2CO3, Solvent
MeO
MeO
Temp.(oC), Time (h)
Yieldb (%)
Temp (oC)
Solvent
Entry
Time (h)
H2O
1
2
3
100
100
100
100
10
10
10
25
DMF
89
88
DMSO
THF
-
4
5
10
10
Toluene
PEG-600
100
100
-
6
7
10
10
90
90
78
PEG-600
80
70
80
80
80
8
9
10
8
PEG-600
PEG-600
PEG-600
PEG-600
90
73
63
6
10
11c
8
a Reaction conditions : 4-methoxy phenylboronic acid (1 mmol),
diphenyldiselenide(0.5 mmol), K2CO3 (1.5 mmol), Cu@PS-TSC
(1.2 mol% of Cu), PEG-600 (4 ml).
b yields refer to those of isolater pure products.
c 0.8 mol % of Cu catalyst was used.
Hence, water and PEG-600 which are both considered as green solvent were chosen for the
phenyl selenylation and phenyl tellurylation of aryl boronic acids, respectively. It was also
speculated that the two units of both (PhSe)2 and (PhTe)2 were consumed in the reaction.
Thus in a typical reaction procedure, a mixture of aryl boronic acid (1 mmol),
diphenyldiselenide (0.5 mmol), K2CO3 (1.5 mmol) and Cu@PS-TSC (1.2 mol% of Cu) were
o
heated in water (4 mL) at 70 C for required period of time (TLC). But for phenyl
tellurylation the reaction of aryl boronic acids (1 mmol) with diphenylditelluride (0.5 mmol)
was carried out in PEG-600 at 80 oC in presence of K2CO3 (1.5 mmol) and Cu@PS-TSC (1.2
mol% of Cu) for a required period of time (TLC).
A wide variety of aryl boronic acids were subjected to react with diphenyldiselenide
to produce a library of aryl-phenyl selenides. The results are summarised in Table 3.
7

Table 3. Cu@PS-TSC catalyzed phenyl selenylation of aryl boronic acids with
diphenyldiselenide in watera
Cu@PS-TSC (1.2 mol% of Cu)
+
R B(OH)2
(PhSe)2
R Se - Ph
K2CO3, H2O, 70 oC
Time(h)
8
R
Yieldb(%) Ref.
Entry
Product
Se
1.
2.
92
80
11f
MeO
MeO
OMe
Se
OMe
OMe
11b
10
9
OMe
Se
3.
4.
5.
88
11f
NO2
NO2
Se
9
8
87
90
11f
7e
OHC
OHC
Se
Br
Br
Se
19
9
91
6.
CN
N
CN
Se
N
3c
9
9
84
83
7
8
Se
11a
aReaction conditins: boronic acids (1 mmol), diphenyl diselenide (0.5 mmol),
K2CO3 (1.5 mmol), Cu@PS-TSC (1.2 mol% of Cu), H2O (4 mL)
bYields refer to those of isolated pure products.
Both electron donating (-OMe) (Table 3, entry 1 and 2) and electron withdrawing (4-
NO2, 4-CHO, 3-Br, 3-CN) (Table 3, entries 3-6) group substituted aryl boronic acids reacted
smoothly with diphenyldiselenide to produce the corresponding organoselenides.
Highly sterically hindered 2,6-dimethoxy phenyl boronic acid also underwent phenyl
selenylation without any difficulty (Table 3, entry 2). 3-Bromophenyl boronic acid after
8

phenyl selenylation produced (3-bromophenyl)(phenyl) selane (Table 3, entry 5) which can
be further converted to various useful molecules by the cross-coupling reaction with an
appropriate coupling partner.16 Heteroaryl substituted boronic acid, i.e. 3-pyridyl boronic acid
after smooth phenyl selenylation produced 3-(phenylselanyl)pyridine (Table 3, entry 7). 2-
Naphthylboronic acid reacted with diphenyldiselenide to produce the corresponding selenide
(Table 3, entry 8) which is an analogue of 5-LOX (Lipoxygenase) inhibitor.17
Similarly a variety of aryl boronic acids were also subjected to react with diphenyldirelluride
under the optimized reaction conditions to obtain a library of aryl-phenyl tellurides. The
results are tabulated in Table 4.
Table 4. Cu@PS-TSC catalyzed phenyl tellurylation of aryl boronic acids with
diphenylditelluride in PEG-600a
Cu@PS-TSC (1.2 mol% of Cu)
R B(OH) +
(PhTe)2
R Te - Ph
2
K2CO3, PEG-600, 80 oC
Yieldb(%) Ref.
R
Time(h)
Entry
Product
Te
1.
2.
87
90
8
8
11g
11b
Te
Te
Te
MeO
OHC
MeO
3.
4.
9
9
11g
18
84
89
OHC
NO2
NO2
Te
Te
8
9
90
88
3g
-
5.
6.
F
F
CF3
CF3
Te
-
10
84
7
MeO
N
MeO
N
aReaction conditins: boronic acids (1 mmol), diphenyl ditelluride (0.5 mmol),
K2CO3 (1.5 mmol), Cu@PS-TSC (1.2 mol% of Cu), PEG-600 (4 mL).
bYields refer to those of isolated pure products.
9

Several functionalities like -OMe, -CHO, -NO2, -F, -CF3 were compatible under the
mild reaction conditions (Table 4, entries 2-6). Heteroaryl substituted boronic acid, i.e. 6-
methoxy-3-pyridyl boronic acid reacted easily with diphenylditelluride to furnish the
corresponding heteroaryl-phenyl telluride (Table 4, entry 7).
In general the reactions are very clean and high yielding. Several functional groups
remain unreacted under the mild reaction conditions. When the reaction was over (TLC), the
product was purified from crude reaction mixture by column chromatography. The atomic
absorption spectroscopy (AAS) of copper content in the final product did not show the
presence of copper which clearly demonstrate that copper was intact to a great extent with the
heterogeneous support and there is no significant amount of leaching occurred during the
reaction. The catalyst Cu@PS-TSCwas successfully recovered by simple filtration through a
cintered glass bed (G-4) and then subsequently washed with ethanol and acetone followed by
o
drying in an oven at 90 C for 6 h before reuse. The catalyst was successfully recycled upto
6th run without any appreciable loss of catalytic activity for both phenyl selenylation and
phenyl tellurylation of 4-methoxy phenyl boronic acid (Figure. 3).
100
80
60
Phenyl selenylation
40
Phenyl tellurylation
20
0
1
2
3
4
5
6
No. of Cycles
Figure 3. Recyclability chart of Cu@PS-TSC catalyst
In conclusion, we have developed a solvent selective methodology for the phenyl
selenylation and phenyl tellurylation of aryl boronic acids catalyzed by a newly synthesized
heterogeneous Cu@PS-TSC catalyst to furnish a wide range of organo mono selenides and
tellurides. The notable advantages offered by this protocol are the use of green solvents such
as water for phenyl selenylation and PEG-600 for phenyl tellurylation, scope for the synthesis
of organoselenides and tellurides, simplicity in operation, general applicability, mild reaction
conditions, compatibility of a wide range of functionalities including the pyridine moiety, use
of a new synthesized recyclable catalyst, high yield of product using a low catalyst loading
10

(1.2 mol% of Cu) which implies high Turn Over Number (TON) of the catalyst, utilization of
both the unit of (PhSe)2 or (PhTe)2 in the reaction which implies that the reaction is atom
economic, high purity of the product etc. These advantages make this procedure green and
cost effective. To the best of our knowledge, we are not aware of such kind of solvent
selective phenyl selenylation and tellurylation of aryl boronic acids with a greener
perspective. Hence we believe that this methodology will be an important addition to the
existing methods for the synthesis of organoselenides and tellurides with respect to green
chemistry.
Acknowledgements
SMI acknowledges Department of Science and Technology (DST) and Council of Scientific
and Industrial Research (CSIR) New Delhi, India for funding. We also acknowledge DST
&UGC, Govt of India for providing support to the Department of Chemistry, University of
Kalyani under PURSE, FIST and SAP programme.
Supplementary Material
1
13
Representative experimental procedures, characterization data, copies of H NMR and C
NMR spectra of all products listed in Table 3 and 4 are given in this section.
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Solvent selective phenyl selenylation and phenyl tellurylation of
aryl boronic acids catalyzed by Cu(II) grafted functionalized
polystyrene
Susmita Roya, Tanmay Chatterjee*b and S.M. Islam*a
aDepartment of Chemistry, University of Kalyani, Nadia, 741235, West Bengal, India.
bDepartment of Organic Chemistry, Indian Association for the Cultivation of Science,
Kolkata-700032, India.
Research Highlights



A new polymer supported copper(II) catalyst has been synthesized and characterized.
Solvent selective Phenyl selenylation and phenyl tellurylation of aryl boronic acids.
Phenyl selenylation in H2O and Phenyl tellurylation in PEG-600 solvent.
 Hazardous organic solvents throughout the reaction were avoided.
 This catalyst can be recycled upto six times.

Graphical abstract
Solvent selective phenyl selenylation and phenyl tellurylation of aryl
boronic acids catalyzed by Cu(II) grafted functionalized polystyrene
Susmita Roy a, Tanmay Chatterjee* b and S.M. Islam* a
Cu@PS-TSC
H2O
R-Se-Ph
(PhSe)2
80-92%
R-B(OH)2
Ph(Te)2
R-Te-Ph
84-90%
PEG-600
K2CO3
R = aryl, heteroaryl