A general and green procedure for the synthesis of organochalcogenides by CuFe2O4 nanoparticle catalysed coupling of organoboronic acids and dichalcogenides in PEG-400

Article abstract of DOI:10.1039/c2ra22415a

A general and efficient procedure has been developed for the synthesis of organochalcogenides (selenides and tellurides) by a simple reaction of organoboronic acids and dichalcogenides catalysed by CuFe₂O ₄ nanoparticles in PEG-400 without any ligand. This protocol offers the scope for access to a wide spectrum of chalcogenides including diaryl, aryl-heteroaryl, aryl-styrenyl, aryl-alkenyl, aryl-allyl, aryl-alkyl and aryl-alkynyl versions. The catalyst is magnetically separable and recyclable eight times without any loss of appreciable catalytic activity. The products are obtained in high purities after evaporation of solvent followed by filtration column chromatography. The Royal Society of Chemistry.

Full text of DOI:10.1039/c2ra22415a

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A general and green procedure for the synthesis of
organochalcogenides by CuFe2O4 nanoparticle
catalysed coupling of organoboronic acids and
dichalcogenides in PEG-4003
Cite this: RSC Advances, 2013, 3, 117
Debasish Kundu, Nirmalya Mukherjee and Brindaban C. Ranu*
A general and efficient procedure has been developed for the synthesis of organochalcogenides (selenides
and tellurides) by a simple reaction of organoboronic acids and dichalcogenides catalysed by CuFe2O4
nanoparticles in PEG-400 without any ligand. This protocol offers the scope for access to a wide spectrum
of chalcogenides including diaryl, aryl–heteroaryl, aryl–styrenyl, aryl–alkenyl, aryl–allyl, aryl–alkyl and aryl–
alkynyl versions. The catalyst is magnetically separable and recyclable eight times without any loss of
appreciable catalytic activity. The products are obtained in high purities after evaporation of solvent
followed by filtration column chromatography.
Received 5th October 2012,
Accepted 29th October 2012
DOI: 10.1039/c2ra22415a
www.rsc.org/advances
addressed primarily the synthesis of aryl–aryl selenides and
tellurides. The coupling with alkyl boronic acids was not
1. Introduction
successful10a,10d except for one case in the presence of
ligand,10e and coupling with heteroaryl, allyl, alkenyl and
alkynyl boronic acids was not addressed. Moreover, a high
temperature and long reaction period were employed. Thus a
green and convenient protocol for the synthesis of these
compounds with general applicability and high efficiency is of
much importance.
The organochalcogenides (selenides and tellurides) have
received renewed interest as these compounds play an
important role in organic synthesis as useful intermediates1
and in pharmaceutical industries for their potential biological
activities such as antiviral, antihypertensive, antioxidant,
antimicrobial and anticancer properties.2 They have important
applications as materials too.3 Thus several methods have
been developed for their synthesis, primarily through transi-
tion metal catalysed aryl–chalcogen bond formation.4 Various
metals including palladium,5 nickel,6 and copper7 have been
employed to catalyze the aryl–chalcogen bond forming
reaction by treatment of aryl halides with thiol and selenol/
PhSeNa under basic conditions. However, because of the
instability and toxicity of these reagents, chalcogenide synth-
esis by the reaction of stable and easily available diaryl
dichalcogenides and aryl halides is widely employed.8 The
organoboronic acids have received much attention as a
reagent of choice because of their easy accessibility, stability,
nontoxicity and compatibility with a variety of functional
groups.9 Thus, a few metal-catalysed aryl carbon–chalcogen
bond forming reactions using aryl boronic acids have been
We recently reported a procedure for the synthesis of diaryl
chalcogenides by a reaction of aryl diazonium fluoroborate
and diaryl dichalcogenides in the presence of Zn in dimethyl
carbonate.11 However, this procedure is limited for access to
diaryl chalcogenides only. Thus to have a better and more
general method we report here a CuFe2O4 nanoparticle12
catalysed coupling of boronic acid with ditellurides and
diselenides in PEG-400 (polyethylene glycol-400) in the
presence of DMSO as an additive (Scheme 1).
2. Results and discussion
To standardise the reaction conditions a series of experiments
were performed under varying reaction parameters such as
solvent, temperature, time and additive for a representative
reaction of 4-methoxyphenyl boronic acid and diphenyl
ditelluride in the presence of CuFe2O4 nanoparticles. Among
a number of solvents such as DMSO, DMF, NMP, CH3CN,
toluene, EtOH and dioxane (Table 1, entries 1–8) studied in the
first phase, DMSO was found to provide the best yields in a
relatively short period of 10 h. However, we sought to have a
greener reaction medium than DMSO and we found that PEG-
reported.10 These include iron,10a CuI,10b CuO nanoparticle,10c
10d
and InBr3
catalysed couplings of aryl boronic acids with
diselenides and ditellurides. Notably, these reactions
Department of Organic Chemistry, Indian Association for the Cultivation of Science,
Jadavpur, Kolkata, 700 032, India. E-mail: ocbcr@iacs.res.in; Fax: +913324732805;
Tel: +913324734971
Electronic Supplementary Information (ESI) available: 1H and 13C NMR spectra
3
of all products. See DOI: 10.1039/c2ra22415a
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Table 1 Standardization of reaction conditions
Entry
Solvent
T/uC
Time/h
Yield (%)a
Scheme 1 Coupling of boronic acids with diaryl diselenides and ditellurides.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
DMSO
DMSO
DMF
NMP
100
80
10
20
20
20
20
20
20
20
20
10
10
10
10
10
10
95
—
30
38
52
36
42
—
28
32
96b
100
100
100
100
100
100
100
100
100
100
100
100
100
400 (polyethylene glycol) in combination with a small amount
of DMSO as an additive furnished a high yield of product in 10
h (Table 1, entry 11). The use of DMSO as an additive in
glycerol required 30 h for completion of a similar reaction.10b
The reaction in PEG-400 in the absence of DMSO gave only
32% yield. The amount of DMSO was optimised to 1.5
equivalents with respect to the boronic acid for the best
results. The reaction did not initiate at all in the absence of
CuFe2O4 catalyst. The amount of catalyst was optimised to 10
mol%. The PEG-400 was also found to work better than PEG-
600 (Table 1, entry 15). Thus, in a typical experimental
procedure, a mixture of an organoboronic acid and diphenyl
ditelluride in PEG-400 was heated at 100 uC in the presence of
CH3CN
Toluene
EtOH
Dioxane
DMC
PEG-400
PEG-400
PEG-400
PEG-400
PEG-400
PEG-600
c
—
78b,d
80e
84b
Yields of isolated pure products with 0.1 mmol catalyst loading (1H
a
and 13C). 1.5 mmol DMSO was used. No catalyst was used. 0.05
mmol catalyst was used. 1.0 mmol of DMSO was used.
b
c
d
e
Table 2 CuFe2O4 nanoparticle catalysed coupling of boronic acids with diphenyl ditelluride
Entry
1
R
Product
Yield (%)a
96
Time/h
10
Ref.
(4-OMe-C6H4)–
10a
2
3
4
(4-COMe-C6H4)–
(4-COOEt-C6H4)–
(3-NHCOMe-C6H4)–
92
90
92
12
10
10
11
11
—
5
(2-CHO-C6H4)–
86
10
16a
6
7
(2-naphthyl)–
94
93
10
12
16b
16c
(2,4,6-trimethyl-C6H2)–
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Table 2 (Continued)
8
(2-NO2-C6H4)–
79
73
12
12
11
11
9
(2-OH-C6H4)–
10
11
(2-SMe-C6H4)–
(4-CN-C6H4)–
90
89
10
11
—
11
12
(3-pyridinyl)–
87
10
16d
13
14
(4,49-biphenyl)–
85
12
12
16e
16f
(n-pentenyl)–(E : Z = 30 : 70)
82 (E : Z = 30 : 70)
15
16
(styryl)–
81
78
12
12
10e
16g
(4-methylstyryl)–
17
18
(phenyl acetenyl)–
(3-thiophenyl)–
82
85
12
10
16h
—
19
20
(4-Me-C6H4)–
90
92
10
10
11
11
(4-OCF3-C6H4)–
a
Isolated yields of pure products (1H and 13C).
CuFe2O4 as the catalyst and DMSO as an additive for the
required period of time (TLC). Extraction of crude product by
ethyl acetate followed by evaporation of solvent and column
chromatography provided the pure product. This procedure
was also found to work efficiently for the reactions of boronic
acid and diphenyl diselenide, boronic esters and diphenyl
ditelluride/diselenide, trifluoroborates and diphenyl ditellur-
ide/diselenide. The CuFe2O4 nanoparticles were commercially
available (Aldrich) and were of 20 nm size.
A wide range of diversely substituted organoboronic acids
underwent reactions with diphenyl ditelluride by this proce-
dure to produce the corresponding organotellurides. The
results are summarized in Table 2. Several electron-with-
drawing groups such as COMe, COOEt, NO2, CHO, CN,
NHCOMe and electron-donating functionalities including
OMe, OCF3, OH on the phenyl ring of the boronic acids are
compatible in this reaction and the yields and reaction time
remained uniform irrespective of the nature of the substitu-
ents. The heteroaryl boronic acids (Table 2, entries 12 and 18)
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Table 3 CuFe2O4 nanoparticle catalysed coupling of boronic acids with diphenyl diselenide
Entry
1
R
Product
Yield (%)a
92
Time/h
Ref.
11
(C6H5)–
12
2
3
(2-OH-C6H4)–
79
90
12
16i
(2-CHO-C6H4)–
12
12
10
10a
4
5
(3,5-dimethyl-C6H3)–
(1-naphthyl)–
86
92
8c
11
6b
(C6H5)–
95
83
87
10
10
12
11
7
(3-pyridinyl)–
(3-quinoline)–
16d
16j
8
9
(2-thiophenyl)–
(2-CN-C6H4)–
89
87
10
12
8c
8c
10
11c
12d
(4-Cl-C6H4)–
(allyl)–
83
78
12
12
16k
8c
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Table 3 (Continued)
13
14
15
(n-butyl)–
83
11
12
12
8c
16l
16g
(n-pentenyl)–(E : Z = 30 : 70)
87 (E : Z = 30 : 70)
(4-methyl styryl)–
80
16
17b
18b
(phenyl acetenyl)–
(phenyl acetynyl)–
(methyl)–
83
78
87
12
12
12
16h
16h
16m
19e
(C6H5)–
87
12
10e
a
b
c
d
Isolated yields of pure products (1H and 13C). Di-(4-methoxyphenyl)-diselenide was used. Di-(4-chlorophenyl)-diselenide was used. Di-(4-
e
methylphenyl)-diselenide was used. Dimethyl diselenide was used.
which were not addressed in telluride coupling earlier,10 also
underwent facile reaction to provide the corresponding
products. The reaction of alkenyl and alkynyl boronic acids
with diphenyl ditellurides provided equally high yields of
products (Table 2, entries 14, 15, 16 and 17). A hindered 2,4,6-
trimethylphenyl boronic acid also underwent coupling with no
difficulty (Table 2, entry 7). The 4,49-biphenyl diboronic acid
provided the corresponding bis-telluride (Table 2, entry 13)
which might be of potential interest as this class of
compounds shows antioxidant properties.13 The styrenyl and
phenyl acetylene tellurides (Table 2, entries 15–17) obtained
easily by this procedure may be of interest in the pharmaceu-
tical industry.14,15
The substituted phenyl boronic acids, when subjected to
reactions with diphenyl diselenides by this procedure,
produced the corresponding organoselenides. The results are
reported in Table 3. A wide range of electron withdrawing and
electron donating substituents on the phenyl ring of boronic
acids are well tolerated in this reaction too. As in telluride
synthesis, a series of diaryl, aryl-heteroaryl, aryl-alkenyl, aryl-
alkynyl unsymmetric selenides were obtained efficiently by
this procedure. The reactions of alkyl boronic acids which
were not successful in absence of ligand by other procedur-
es10a,10b were achieved efficiently by our protocol (Table 3,
entries 13 and 18). The reaction of dialkyl diselenide and
phenyl boronic acid also proceeded without any difficulty by
this protocol (Table 3, entry 19). Significantly, both electron
withdrawing and electron donating group substituted diphe-
nyl diselenides participated in this reaction (Table 3, entries 6,
11 and 18).
To expand the scope of this coupling, boronic esters and
trifluoroborates were also employed as alternatives to boronic
acid in these tellurylation and selenylation reactions. Several
substituted boronic acid pinacol esters and aryl trifluorobo-
rates underwent reactions with diphenyl ditellurides and
diselenides by the same procedure to produce the correspond-
ing products. The coupling of boronic esters is summarized in
Table 4 and that of trifluoroborates is presented in Table 5.
In general, the reactions are very clean and high yielding.
All the reactions are complete within 10–12 h except for those
of boronic acid pinacol esters (16–18 h). The products are
obtained in high purity just by filtration chromatography. The
nature and position of the substituents did not have any effect
on the reaction rates and yields. Functionalization of products
with a wide range of groups such as OMe, COOEt, COMe,
CHO, CN, NO2, OCF3, SMe, NHCOMe, Cl, F has been
successfully achieved by this procedure. Thus this procedure
offers scope for further manipulation of products. The
CuFe2O4 nanoparticle catalyst is recyclable up to eight runs
without any considerable loss of reactivity (Fig. 1). However,
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Table 4 Coupling of diphenyl diselenides/ditellurides with boronic acid pinacol
Table 5 Coupling of diphenyl diselenides/ditellurides with aryl trifluoroborates
esters
Entry
1
R
Product
Yield (%)a Time/h Ref.
4-OMe
92
10
11
Entry
1
R
Product
Yield (%)a Time/h Ref.
4-OMe
92
88
80
71
16
18
18
18
11
11
11
11
2
4-Me
88
12
11
2
3
4
4-Me
4-F
3
4
H
87
80
12
12
11
11
4-COMe
2-NO2
a
Isolated yields of pure products (1H and 13C).
5
6
H
89
91
18
16
11
11
although iron may have some role in enhancing the catalytic
activity of Cu.
A possible reaction pathway is outlined in Scheme 2.
Initially, in cycle I the CuFe2O4 nanoparticle undergoes
oxidative addition to diphenyl ditelluride/diselenide to form
an intermediate A which then undergoes transmetallation
with phenyl boronic acid to provide the intermediate B. In a
subsequent step this intermediate leads to the product, with
telluride/selenide regenerating the catalyst via reductive
elimination. On the other hand in cycle II the boronic acid
interacts with CuFe2O4 to form the intermediate C which then
reacts with [PhTe]2, another half of Ph2Te2 leading to B which
4-OMe
a
Isolated yields of pure products (1H and 13C).
after each cycle the CuFe2O4 nanoparticles which were initially
of 20 nm size grew slightly bigger because of their inherent
agglomeration tendency. After the 8th cycle, the particles
attained 78 nm sizes and their catalytic activity was reduced
substantially (Fig. 2).
A recent report10f described C–Se bond formation by
reaction of PhSeBr and organoboronic acids catalysed by
CuFe2O4. However, our work deals with the reaction of
commercially available and robust diphenyldiselenides/tell-
urides with boronic acids involving both selenide/telluride
moieties. Thus it is essentially different and more practical as
it uses diaryl dichalcogenides directly. Notably, PhSeBr was
obtained from PhSeSePh.
To have an understanding of the active catalytic centre on
CuFe2O4, when the reaction of diphenyl ditelluride and
4-methoxyphenyl boronic acid was performed using Fe3O4
nanoparticles the progress of the reaction was found to be only
25% in 12 h time. Thus, it is more likely that copper is the
active catalytic centre as observed in similar reactions,10b,10c,10e
Fig. 1 Recyclability of the catalyst.
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microtek Qtof Micro YA263 spectrometer. The size of the
nanoparticles (catalyst) was determined by HR-TEM experi-
ment. All commercial reagents were distilled before use.
CuFe2O4 nanoparticle, DMSO (dimethylsulfoxide), PEG-400
(polyethylene glycol- 400), boronic acids, boronic esters and
trifluoroborates were purchased from Aldrich.
Representative experimental procedure for the reaction of
4-methoxyphenyl boronic acid and diphenyl ditelluride
(Table 2, entry 1)
A mixture of 4-methoxyphenyl boronic acid (152 mg, 1 mmol),
diphenyl ditelluride (200 mg, 0.5 mmol), CuFe2O4 nanoparti-
cles (24 mg, 0.1 mmol) and DMSO (120 mg, 1.5 mmol) in PEG-
400 (3 mL) was heated at 100 uC for 10 h (TLC). After being
cooled to room temperature the reaction mixture was extracted
with ethyl acetate and the extract was evaporated to give the
crude product which was purified by column chromatography
to provide the product as a white solid (299 mg, 96%), mp 60–
62 uC, IR (KBr) 3062, 1880, 1585, 1488 cm21 1H NMR (500
;
MHz, CDCl3) d 3.76 (s, 3H), 6.78 (d, J = 8.5 Hz, 2H), 7.13–7.19
(m, 3H), 7.55 (d, J = 7.5 Hz, 2H), 7.71 (d, J = 8.5 Hz, 2H); 13C
NMR (125 MHz, CDCl3) d 55.2, 103.3, 115.6 (2C), 116.0, 127.4,
129.4 (2C), 136.5 (2C), 141.3 (2C), 160.1. These data are in good
agreement with the reported values11 for (4-methoxyphenyl)(-
phenyl)tellane.
Fig. 2 TEM images of CuFe2O4 NPs.
This procedure was followed for all the reactions in Tables 2,
3, 4 and 5. A few of these products are known compounds (see
the references in Tables 2, 3, 4 and 5) and were easily
identified by comparison of their spectroscopic data with
those previously reported. The unknown compounds were
finally produces the product. Thus both telluride/selenide
moieties of (PhTe)2/(PhSe)2 are consumed in the reaction,
making it atom-efficient. The DMSO present in the reaction
mixture is reduced to dimethyl sulfide under the reaction
conditions and it is assumed that dimethyl sulfide stabilizes
the boronic acid formed in the transmetallation step and thus
the presence of DMSO accelerates the process.10d
1
fully characterized by their IR, H NMR, 13C NMR and HRMS
spectra, and C, H, N-analyses. These data are given below in
order of their entries in Table 2.
N-(3-(Phenyltellanyl)phenyl)acetamide (Table 2, entry 4)
Yellow viscous liquid; IR (neat) 3296, 3257, 3064, 2991, 2850,
1668, 1581 cm21 1H NMR (300 MHz, CDCl3) d 2.08 (s, 3H),
;
7.08–7.28 (m, 4H), 7.37 (d, J = 7.34 Hz, 1H), 7.52 (d, J = 7.90 Hz,
1H), 7.68 (d, J = 7.01 Hz, 2H), 7.77 (s, 1H), 8.13 (s, 1H); 13C
NMR (75 MHz, CDCl3) d 24.4, 114.5, 115.1, 119.7, 128.0, 128.9,
129.6 (2C), 129.9, 133.5, 138.2 (2C), 138.8, 169.1; HRMS calcd.
for C14H13OTe [M + Na]+: 363.9957; Found: 363.9926.
3. Experimental
IR spectra were recorded on a Shimadzu 8300 FTIR spectro-
meter. 1H-NMR and 13C-NMR spectra were run on Bruker DPX-
300 and DPX-500 instruments. HRMS were acquired on a
Scheme 2 Possible mechanism
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1
Yellow liquid; IR (neat) 3049, 2916,1562, 1433 cm21; H NMR
(500 MHz, CDCl3) d 2.42 (s, 3H), 6.84 (t, J = 8.0 Hz, 1H), 6.96 (d,
J = 7.5 Hz, 1H), 7.07 (t, J = 7.5 Hz, 1H), 7.12–7.24 (m, 3H), 7.31
(t, J = 7.5 Hz, 2H), 7.79 (d, J = 8.0 Hz, 1H); 13C NMR (125 MHz,
CDCl3) d 19.3, 115.0, 124.5, 127.8, 128.8, 129.9 (2C), 130.1,
134.3 (2C), 140.5, 140.7; anal calc. for C13H12STe: C 47.62, H
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3-Phenyltellanyl-thiophene (Table 2, entry 18)
1
Yellow liquid; IR (neat) 3064, 2989, 1573, 1473 cm21; H NMR
(500 MHz, CDCl3) d 7.19–7.31 (m, 5H), 7.59–7.62 (m, 3H); 13C
NMR (125 MHz, CDCl3) 104.0, 115.4, 127.3, 127.9, 129.5 (2C),
134.6, 136.6 (2C), 136.9; anal calc. for C10H8STe: C 41.73, H
2.80; found: C 41.66, H 2.92%.
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Procedure for recyclability of catalyst
After completion of the reaction the magnetic bar covered with
the used catalyst was collected by a magnetic rod and the bar
was successively washed with ethanol and acetone before
being poured into another reaction pot for the next cycle of
reaction.
4. Conclusion
In conclusion, we have developed an efficient procedure for
the synthesis of organotellurides and selenides by the reaction
of boronic acid/boronic ester/trifluoroborate with diphenyl
ditelluride/diselenide catalysed by CuFe2O4 nanoparticles in
PEG-400 in the presence of a small amount of DMSO as an
additive. The simplicity in operation, general applicability to
various types of boronic acids including heteroaryl, alkynyl,
alkenyl and particularly alkyl boronic acids which were
reported to be inactive,10a,10d and wide scope of the functio-
nalization make this protocol more attractive than the existing
ones. In addition, recyclability of the catalyst for eight runs,
use of PEG-400 as the reaction medium and high yields of
products in a relatively short period make this procedure
greener and more cost effective. We believe, this will provide a
practical solution to the synthesis of difficult to access
organotellurides and selenides.
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Acknowledgements
We are pleased to acknowledge the financial support from
DST, New Delhi under J. C. Bose Fellowship grant (SR/S2/JCB-
11/2008) to B. C. Ranu. DK thanks CSIR, New Delhi for his
fellowship. We acknowledge support of Nanoscience Project
Unit at IACS, funded by DST, New Delhi.
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