Alternative Metal-Free Synthesis of Diorganoyl Selenides and Tellurides Mediated by Oxone

Article abstract of DOI:10.1055/s-0036-1591992

We herein describe an alternative metal-free methodology for the synthesis of diorganyl selenides and tellurides mediated by Oxone . The products were obtained in moderate to excellent yields by reactions of diorganyl diselenides or ditellurides with aryl boronic acids mediated by Oxone with use of EtOH as the solvent. The methodology is applicable to a broad scope of diorganyl dichalcogenides and aryl boronic acids containing electron-rich, electron-poor, and sterically hindered substituents.

Full text of DOI:10.1055/s-0036-1591992

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© Georg Thieme Verlag Stuttgart · New York
2018, 29, A–F
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A
en
G. Perin et al.
Letter
Synlett
Alternative Metal-Free Synthesis of Diorganoyl Selenides and Tel-
lurides Mediated by Oxone®
Gelson Perin*a
Luis Fernando B. Duartea
José S. S. Netoa
Márcio S. Silvab
Diego Alves*a
Oxone®, EtOH
60 °C, air
Y
R
Y
Ar B(OH)2
+
R
Y
R
Ar
Y = Se, Te
R = aryl, alkyl
18 examples (37–98% yield)
metal-free
mild reaction conditions
a Laboratório de Síntese Orgânica Limpa – LASOL, CCQFA, Universidade Federal de Pelotas
– UFPel, PO Box 354, 96010-900, Pelotas, RS, Brazil
gelson_perin@ufpel.edu.br
diego.alves@ufpel.edu.br
b Centro de Ciências Naturais e Humanas – CCNH, Universidade Federal do ABC – UFABC,
09210-580, Santo André, SP, Brazil
Received: 21.03.2018
Accepted after revision: 22.03.2018
Published online: 23.04.2018
become a versatile tool for the synthesis of diaryl chalco-
genides.6 In some cases, these transition metal-catalyzed
reactions involve particularly specific ligands, which may
increase the cost and limit the scope of applications, the use
of high temperatures, and the presence of environment-ag-
gressive solvents.6 Considering the aforementioned, there is
a great interest in the development of new and environ-
mentally benign methodologies for the synthesis of organo-
chalcogen compounds.
In this way, potassium peroxymonosulfate, known as
trademark Oxone®, has been explored since its first patent
registration in 1957.7 This white solid, an easy-to-handle,
nontoxic, and cheap compound, is commercially available
in a triple salt form (2KHSO5·KHSO4·K2SO4) and has been
used for more than fifty years for a range of organic trans-
formations.8 For example, Prasad and coworkers exploring
metal-free sulfenylation of 1H-indoles demonstrated the
use of Oxone® to generate electrophilic sulfur species.9
However, the use of Oxone® in the chemistry of organochal-
cogen compounds,10 more specifically in selenium and tel-
lurium compounds, is poorly explored.
In view of the explained above and according to our in-
terest in the development of environmentally benign pro-
tocols correlated to the synthesis of organochalcogen com-
pounds,1a we assumed that Oxone® could be a mild oxidant
to generate electrophilic organochalcogen species. Thus, we
report here our results on the synthesis of diorganoyl chal-
cogenides by reaction of diorganyl dichalcogenides with
aryl boronic acids mediated by Oxone® with use of EtOH as
solvent (Scheme 1).
DOI: 10.1055/s-0036-1591992; Art ID: st-2018-v0109-l
Abstract We herein describe an alternative metal-free methodology
for the synthesis of diorganyl selenides and tellurides mediated by
Oxone®. The products were obtained in moderate to excellent yields by
reactions of diorganyl diselenides or ditellurides with aryl boronic acids
mediated by Oxone® with use of EtOH as the solvent. The methodology
is applicable to a broad scope of diorganyl dichalcogenides and aryl bo-
ronic acids containing electron-rich, electron-poor, and sterically hin-
dered substituents.
Key words organoselenium compounds, Oxone®, green chemistry,
diaryl selenides, aryl boronic acids
Organochalcogen compounds, emphasizing those con-
taining selenium and tellurium, are considered an import-
ant class of chemical entities, and their chemistry, toxicolo-
gy, and pharmacology are well described in a great number
of reviews1 and books.2 The synthesis of symmetric and un-
symmetric organochalcogen compounds is a field of great
interest owing to their special structural motifs and unique
reactivity. For example, organochalcogen compounds serve
as highly powerful and valuable building blocks in the syn-
thesis of natural products3 and selective transformations1,2,4
as well, as these compounds are often linked to pharmaco-
logical activities.1,2,5
This point has motivated the development of different
methodologies to synthesize these compounds. Regarding
the selenium or tellurium species used as starting materi-
als, the large number of methods to prepare these com-
pounds can be classified in two main categories: (a) those
that use electrophilic organochalcogen and (b) those using
nucleophilic organochalcogen species. Alternatively, reac-
tions of diaryl dichalcogenides with aryl halides or organo-
boron species catalyzed by transition metals, such as cop-
per, indium, palladium, iron, silver, and iridium salts, have
Oxone®, EtOH
Y
R
Y
+
Ar
B(OH)2
R
Y
R
Ar
60 °C, air
Y = Se, Te
R = aryl, alkyl
Scheme 1 General scheme of the present work
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

B
G. Perin et al.
Letter
Synlett
At first, diphenyl diselenide (1a), 4-methoxyphenyl-
boronic acid (2a), and Oxone® were selected as a model sys-
tem to optimize the reaction conditions. Thus, we started
studying the reaction of substrates 1a (0.15 mmol) and 2a
(0.3 mmol) in the presence of Oxone® (0.15 mmol) using
0.5 mL of EtOH as the solvent at room temperature in air.
Under these reaction conditions, the desired selenide 3a
was obtained in 61% yield after 24 h (Table 1, entry 1).
When this reaction was carried out at 60 °C, the product
was formed in 72% yield (Table 1, entry 2).
of Oxone® (Table 1, entry 4 versus 6). Therefore, it was de-
cided to use 0.3 mmol of Oxone® for further studies on opti-
mizing the reaction conditions.
Several solvents were tested in place of EtOH. When the
reactions were performed with use of EtOAc, hexane,
MeCN, H2O, and glycerol, only trace amounts of the desired
product 3a were observed (Table 1, entries 7–11). PEG-400
was not a good solvent for this reaction, affording selenide
3a in only 32% yield (Table 1, entry 12). In addition, when
we used a mixture of EtOH/H2O (1:1) as a solvent system,
the formation of product 3a was observed in 39% yield (Ta-
ble 1, entry 13).
Table 1 Optimization of the Reaction Conditionsa
To our delight, a substantial increase in the chemical
yield of compound 3a was achieved when the reaction was
performed in dry EtOH at 60 °C (Table 1, entry 14). It is im-
portant to note that when this reaction was performed at
room temperature, 84% yield of the selenide 3a was ob-
tained (Table 1, entry 15); also a decrease in the amount of
Oxone® from 0.3 to 0.15 mmol substantially affected the re-
action yield (Table 1, entry 16).
Finally, to obtain an efficient methodology in terms of
energy economy, we performed a study to establish the
minimum time associated with a good reaction rate under
the aforementioned optimized conditions (Scheme 2). Ana-
lyzing Scheme 2, excellent conversion of diphenyl disele-
nide (1a) and 4-methoxylphenylboronic acid (2a) into 4-
methoxyphenyl-phenyl-selenide (3a) was observed after
two hours of reaction.
Oxone®
solvent
B(OH)2
Se
Se
+
Se
temperature
24 h, air
MeO
MeO
1a
2a
3a
Entry
Oxone® (mmol) Solvent
Temperature
Yield (%)
1
2
0.15
0.15
0.3
EtOH
r.t.
60
r.t.
60
reflux
60
60
60
60
60
60
60
60
60
r.t.
60
61
EtOH
72
3
EtOH
77
4
0.3
EtOH
86
5
0.3
0.45
0.3
EtOH
87
6
EtOH
90
7
EtOAc
hexane
MeCN
glycerol
H2O
traces
traces
traces
traces
traces
32
8
0.3
9
0.3
10
11
12
13
14b
15b
16b
0.3
0.3
0.3
PEG-400
EtOH/H2O (1:1)
EtOH
0.3
39
0.3
98
0.3
EtOH
84
0.15
EtOH
78
a Reactions were carried out in the presence of diphenyl diselenide (1a)
(0.15 mmol), p-methoxylphenyl boronic acid (2a) (0.3 mmol), with 0.5 mL
of solvent in air.
b The reaction was carried out with use of dry EtOH (0.5 mL).
Scheme 2 Plot of conversion versus time for the synthesis of selenide 3a
Aiming to improve the yield of selenide 3a, we decided
to increase the amount of Oxone®. When the reaction was
performed at room temperature with use of 0.3 mmol of
Oxone®, the desired product 3a was obtained in 77% (Table
1, entry 3), while the reaction carried out at 60 °C yielded
selenide 3a in 86% (Table 1, entry 4). A similar yield of prod-
uct 3a was obtained when the reaction was performed un-
der reflux (Table 1, entry 5). When the reaction was carried
out with 0.45 mmol of Oxone®, the desired product 3a was
obtained in 90% yield after 24 hours (Table 1, entry 6). We
observed that the yields of product 3a were almost the
same in reactions performed with use of 0.3 or 0.45 mmol
Having the best reaction conditions established, we ex-
plored the efficiency and generality of our methodology.11
The scope of our methodology was evaluated by reactions
of other substituted aryl boronic acids 2b–i with diphenyl
diselenide (1a), and according to our results, moderate to
good yields were obtained for a variety of substrates (Table
2, entries 2–9). In a general way, the reactions are sensitive
to the electronic effect of the aromatic ring in the aryl bo-
ronic acids 2a–i. For example, aryl boronic acids containing
electron-donating groups (EDG) at the aromatic ring gave
higher yields than those bearing electron-withdrawing
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

C
G. Perin et al.
Letter
Synlett
(EWG) and electron-neutral groups (Table 2, entries 1–4
versus 5–9). Only traces of product 3f were observed by us-
ing 2-chlorophenylboronic acid (2f) as a substrate, even af-
ter 24 hours (Table 2, entry 6). When 3-thienylboronic acid
(2j) was used as a substrate, the respective product 3x was
obtained in a lower yield (Table 2, entry 10). An explanation
for these moderate yields is that these less reactive aryl
boronic acids 2e–j, in the presence of Oxone®, could be oxi-
dized to the respective boroximes and alcohols.12 These re-
actions were also performed under a N2 atmosphere and no
increase in the reaction yields were observed.
Table 2 Scope and Generality in the Synthesis of Selenides 3 Mediated by Oxone®.a
Oxone®, EtOH
60 °C, air
Se
Se
R
Ar B(OH)2
+
R
Ar
R
Se
1a–i
2a–j
3a–r
Entry
1
Diorganoyl diselenide 1
Aryl boronic acid 2
Time (h)
2
Product 3 (Yield)
Se
B(OH)2
Se
Se
OMe
MeO
3a
(98%)b
2a
1a
OMe
OMe
Se
B(OH)2
Se
Se
2
2
3b
1a
2b
(95%)
Se
B(OH)2
Se
Se
3
4
5
6
6
3c
2c
1a
(84%)
Se
B(OH)2
Se
Se
3d
(78%)
1a
2d
Se
B(OH)2
Se
Se
24
Cl
Cl
3e
2e
1a
(40%)
Cl
Cl
Se
B(OH)2
Se
Se
6
7
8
24
3f
(traces)
1a
2f
Se
B(OH)2
Se
Se
4
Br
Br
3g
2g
1a
(61%)
Br
Br
Se
B(OH)2
Se
Se
4
3h
1a
2h
(67%)
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

D
G. Perin et al.
Letter
Synlett
Table 2 (continued)
Entry
Diorganoyl diselenide 1
Aryl boronic acid 2
Time (h)
24
Product 3 (Yield)
Se
B(OH)2
Se
9
Se
3i
(42%)
2i
1a
Se
B(OH)2
Se
1a
10
11
12
13
14
15
24
4
S
Se
S
3j
(37%)
2j
Se
B(OH)2
Se
Se
OMe
MeO
MeO
MeO
3k
2a
2a
2a
1b
(96%)
OMe
Se
B(OH)2
B(OH)2
B(OH)2
B(OH)2
Se
6
Se
MeO
OMe
3l
(97%)
1c
MeO
F
Se
Se
3
Se
F
OMe
3m
(96%)
1d
F
Se
Cl
Se
2
Cl
OMe
Se
MeO
MeO
3n
2a
2a
(97%)
1e
Cl
F3C
Se
F3C
Se
3
Se
CF3
OMe
3o
1f
(96%)
Se
B(OH)2
Se
Se
16
24
OMe
MeO
2a
3p
1g
(63%)
Se
B(OH)2
B(OH)2
Se
Se
17
18
6
6
OMe
Se
MeO
MeO
1h
3q
2a
2a
(75%)
Se
Se
OMe
1i
3r
(80%)
a Reactions were carried out in the presence of diorganoyl diselenide 1 (0.15 mmol), aryl boronic acid 2 (0.3 mmol), Oxone® (0.3 mmol), with use of 0.5 mL of
dry EtOH at 60°C in air.
b When the reaction was performed with use of diphenyl diselenide (1a) (2.5 mmol), 4-methoxylphenylboronic acid (2a) (5.0 mmol), Oxone® (5.0 mmol), dry
EtOH (10 mL), the desired product 3a was obtained in 90% yield.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F

E
G. Perin et al.
Letter
Synlett
Then, other diorganyl diselenides 1b–i were explored as
substrates. Reactions of different diaryl diselenides contain-
ing electron-donating and electron-withdrawing groups at
the aromatic ring were performed with p-methoxylphenyl-
boronic acid (2a), affording the respective diarylselenides
3k–o in excellent yields (Table 2, entries 11–15). Our results
reveal that the yields are not sensitive to the electronic ef-
fects, since diaryl diselenides containing EDG or EWG af-
forded high yields of the respective products 3k–o (Table 2,
entries 11–15). The reaction appears to be sensitive to ste-
ric effects, and when hindered dimesityl diselenide (1g)
was used, the desired product 3p was obtained in 63% yield
(Table 2, entry 16). Dialkyl diselenides 1h,i reacted with p-
methoxylphenyl boronic acid (2a) in the presence of 0.3
mmol of Oxone® to produce the corresponding selenides
3q,r in 75% and 80% yield, respectively, proving that diaryl
diselenides are not the only suitable substrates for this re-
action (Table 2, entries 17 and 18).
methodology allows the use of a broad scope of diorganyl
dichalcogenides and aryl boronic acids containing electron-
rich, electron-poor, and sterically hindered substituents.
The obtained results indicate that this Oxone®-mediated
carbon−chalcogen bond formation is able to use both
groups on diorganyl dichalcogenides.
Acknowledgment
The authors are grateful to Fundação de Amparo à Pesquisa do Estado
do Rio Grande do Sul (FAPERGS PRONEM 16/2551-0000240-1), Con-
selho Nacional de Desenvolvimento Científico e Tecnológico (CNPq -
Universal 447595/2014-8, PQ 304649/2017-1), and Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for the finan-
cial support.
Supporting Information
Supporting information for this article is available online at
In an attempt to extend the scope of our methodology,
the possibility of performing the reaction with other diaryl
dichalcogenides was investigated (Scheme 3). Thus, 4-me-
thoxyphenylboronic acid (2a) was efficiently treated with
diaryl ditellurides 1j–l, affording the respective diaryl tellu-
rides 3s–u in excellent yields. When the reaction was per-
formed with dibutyl ditelluride (1m), 4-methoxyphenyl-
butyl-telluride (3v) was obtained in 56% yield. Unfortunate-
ly, when the reaction was carried out with diphenyl disul-
fide (1n), the corresponding product 3w was not obtained,
even after 48 hours.
https://doi.org/10.1055/s-0036-1591992.
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References and Notes
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YR
B(OH)2
Oxone®, EtOH
60 °C, air
Y
R
+
R
Y
MeO
MeO
1j–n
3s–w
2a
Y = Te; R = Ph 1j
Y = Te; R = 4-MeC6H4 1k
Y = Te; R = 4-ClC6H4 1l
Y = Te; R = Bu 1m
Y = S; R = Ph 1n
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Te
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OMe
Cl
OMe
3s
92% (5 h)
3u
94% (5 h)
OMe
3t
83% (5 h)
Te
S
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OMe
OMe
3w
nd (48 h)
3v
56% (5 h)
Scheme 3 Reaction scope with other dichalcogenides
In conclusion, we have developed an alternative metal-
free approach for the synthesis of diorganyl chalcogenides.
The products were obtained in moderate to excellent yields
by the reactions of diorganyl diselenides or ditellurides
with aryl boronic acids in the presence of Oxone® with use
of EtOH as solvent at 60 °C under an air atmosphere. The
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(11) General Procedure for the Oxone®-Mediated Synthesis of
Diorganoyl Selenides and Tellurides 3
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To a Schlenk tube equipped with a small magnetic stirring bar
were added the appropriate diorganoyl dichalcogenide (0.15
mmol), the appropriate aryl boronic acid (0.3 mmol), Oxone®
(0.046 g, 0.3 mmol), and dry EtOH (0.5 mL). The resulting
mixture was stirred at 60 °C until the total consumption of the
starting materials. After that, the reaction mixture was cooled
to room temperature and quenched with water (5 mL). Then,
the mixture was extracted with ethyl acetate (10 mL) and
washed with water (3 x 10 mL). The combined organic layers
were dried with anhydrous MgSO4 and concentrated under
vacuum to yield the crude product, which was purified by flash
chromatography on silica gel by using hexane or a mixture of
hexane/ethyl acetate as the eluent.
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n-Octyl-4-methoxylphenyl-selenide (3r)
1
Yield: 0.072 g (80%). H NMR (CDCl3 400 MHz): δ = 7.55 (d, J =
8.8 Hz, 2 H), 6.92 (d, J = 8.8 Hz, 2 H), 3.90 (s, 3 H), 2.92 (t, J = 7.6
Hz, 2 H), 2.70 (quint, J = 7.6 Hz, 2 H), 1.52–1.38 (m, 10 H), 0.98
(t, J = 7.6 Hz, 3 H). 13C NMR (CDCl3 100 MHz): δ = 159.1, 135.4,
120.3 114.7, 55.3, 31.8, 30.2, 29.8, 29.2 (2C), 29.1, 22.6, 14.1.
MS: m/z (%) = 300 (76), 298 (40), 188 (89), 186 45), 108 (100),
57 (31), 343 (38). HRMS: m/z calcd for
C
15H25OSe [M]+:
301.1071; found: 301.1078.
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–F