A simple copper salt-catalyzed synthesis of unsymmetrical diaryl selenides and tellurides from arylboronic acids with diphenyl diselenide and ditelluride

Article abstract of DOI:10.1055/s-2005-871936

In the presence of a catalytic amount of simple copper salt, the reaction of arylboronic acids with diphenyl diselenide and ditelluride was accomplished without any additive to afford the corresponding unsymmetrical diarylselenides and tellurides in good yields. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2005-871936

LETTER
2007
A Simple Copper Salt-Catalyzed Synthesis of Unsymmetrical Diaryl Selenides
and Tellurides from Arylboronic Acids with Diphenyl Diselenide and
Ditelluride
Synthesis of
U
n
e
symmetric
i
S
ele
W
nide
s
and
T
ellurides ang,*a,b Min Wang,a Fuping Huanga
a
Department of Chemistry, Huaibei Coal Teachers College, Huaibei, Anhui 235000, P. R. China
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, P. R. China
Fax +86(561)3090518; E-mail: leiwang@hbcnc.edu.cn
Received 7 June 2005
arylsulfonyl chlorides12 have been demonstrated. Howev-
er, to the best of our knowledge, the reaction of boronic
acids with diphenyl diselenide and ditelluride has not been
disclosed. In this communication, we describe a simple
copper salt catalyzed the reaction of arylboronic acids
with diphenyl diselenide and ditelluride in the absence of
additional ligand and base, which generates the corre-
sponding unsymmetrical diaryl selenides and tellurides in
good yields under mild reaction conditions (Scheme 1).
Abstract: In the presence of a catalytic amount of simple copper
salt, the reaction of arylboronic acids with diphenyl diselenide and
ditelluride was accomplished without any additive to afford the cor-
responding unsymmetrical diarylselenides and tellurides in good
yields.
Key words: copper salt, diaryl selenides, diaryl tellurides, aryl-
boronic acids, diphenyl diselenide, diphenyl ditelluride
Organoselenium and tellurium compounds have received
much attention not only as synthetic reagents or interme-
diates in organic synthesis but also as promising donor
molecules for conductive materials, anticancer and anti-
oxidant agents.1 A number of synthetic methods have
been reported to prepare organoselenium and tellurium
derivatives. A convenient and general method to intro-
duce a selenium or tellurium moiety into organic mole-
cules is the reaction of a metal selenolate or tellurolate
with appropriate electrophiles such as organic halides,
acyl chlorides, epoxides, and a,b-enones.2 However, it is
more difficult to synthesize the unsymmetrical diaryl se-
lenides and tellurides through the reaction of selenide and
telluride anions with aryl halides because of the less reac-
tivity of halides. The reaction of halobenzenes with phe-
nylselenol or benzeneselenolate anion was generally
carried out in the presence of catalyst, ligand and strong
base for accomplishing this transformation.3 In addition,
the reaction often needs long time and harsh reaction con-
ditions and sometimes generates the products in moderate
yields. Therefore, it is desirable to develop more simple
and efficient method to synthesize unsymmetrical diaryl
selenides and tellurides in the absence of additional ligand
and base.
CuI (10 mol%)
DMSO, air
PhZZPh
+
ArB(OH)2
PhZAr
Z = Se, Te
Without any additive!
Scheme 1
Transition metal-catalyzed cross-coupling reactions re-
present an extremely versatile tool in organic synthesis.13
However, only Taniguchi and his co-worker reported a
copper-catalyzed synthesis of unsymmetrical diaryl-
selenides from aryl iodides and diphenyl disenide (accom-
panied with cleavage of the diselenide bond) in the
presence of magnesium metal and bipyridine.14 With the
aim of providing an important procedure for the prepara-
tion of unsymmetrical diaryl selenides and tellurides, we
began to explore the reaction of organoboronic acids with
diphenyl diselenide and ditelluride in the presence of
copper salt.
In our initial studies, we observed that the reaction of
diphenyl diselenide with p-tolylboronic acid in the pres-
ence of CuI (10 mol%, in DMSO, at 100 °C) went
smoothly to generate phenyl p-tolyl selenide in excellent
yield (91%) without the addition of any ligand and base.
The results are summarized in Table 1. Of the simple cop-
per salts we tested in the reaction, CuCl, CuBr, CuSO4,
Cu(OAc)2, and CuCl2 also gave the corresponding prod-
ucts in 64%, 56%, 70%, 67% and 61% yields, respectively
(entries 1–5, Table 1). The amount of cuprous iodide was
also examined. When the amount of cuprous iodide was
less than 1 mol%, only trace product was formed. The
satisfactory results were obtained when the amount of
cuprous iodide was in the range of 5–15 mol%. It is im-
portant to note that the reaction in the absence of copper
salt did not result in the formation of product.
Organoboronic acids are widely used as reagents in organ-
ic synthesis because they are commercially available, sta-
ble, generally non-toxic, and compatible with a variety of
functional groups. Over the past years, the coupling reac-
tions of boronic acids with organic halides,4 phenols,5
amines,6 allyl alcohols,7 imidazoles,8 alkynes,9 alkynes
and imines,10 allenic alcohols,11 aryl arenesulfonates and
SYNLETT 2005, No. 13, pp 2007–2010
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9
.0
8
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0
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5
Advanced online publication: 12.07.2005
DOI: 10.1055/s-2005-871936; Art ID: U17705ST
© Georg Thieme Verlag Stuttgart · New York

2008
L. Wang et al.
LETTER
To select proper solvent is very important in this reaction. ucts were observed (entries 6 and 13). This reaction was
We conducted the reaction of diphenyl diselenide with p- tolerant of ortho-substitution in arylboronic acids (entries
tolylboronic acid in the presence of cuprous iodide under 4, 8 and 14). More remarkable was our observation that
different solvents. Among the solvents we investigated, extremely sterically hindered 2,6-dimethoxyphenylbo-
DMSO proved to be the best solvent of choice. None of ronic acid reacted cleanly with diphenyl diselenide and
the desired products was obtained when the reaction was ditelluride under this reaction conditions (entries 8 and
carried out in DMF, THF, acetonitrile, benzene, methyl- 14). Fortunately, dialkyl diselenide (n-C4H9SeSeC4H9-n)
ene chloride and toluene.
also reacted with p-methoxyphenylboronic acid and p-
tolylboronic acid to generate the corresponding products
in 62% and 68% yields, respectively (entries 16 and 17).
It should be noted that diaryl tellurides are not stable in the
air and they are easily to be oxidized by oxygen (diphe-
nylditelluride and diarylselenides are more stable). The
reaction of arylboronic acids with diphenyl ditelluride
should be performed under inert atmosphere (generally
under nitrogen or argon).
The effect of reaction temperature and reaction time on
the reaction was also surveyed. High yield was obtained
when the reaction was carried out in DMSO at 100 °C for
seven hours. The reaction at room temperature for 48
hours only gave trace amount of the product.
Table 1 Effect of Copper Salt on the Reaction of Arylboronic Acids
with Diphenyl Diselenidea
Cu salt
B(OH)2
SeSe
+
Se
Table 2 CuI-Catalyzed the Reaction of Boronic Acids with
DMSO
Diphenyl Diselenide and Ditelluridea
Entry
1
Copper salt (amount)
CuCl (10 mol%)
CuBr (10 mol%)
CuSO4 (10 mol%)
Cu(OAc)2 (10 mol%)
CuCl2 (10 mol%)
CuI (10 mol%)
CuI (20 mol%)
CuI (15 mol%)
CuI (7.5 mol%)
CuI (5 mol%)
Yield (%)b
Entry ArB(OH)2
RZZR
Yield (%)b
91
64
56
70
67
61
91
90
91
92
89
45
15
N.r.
1
2
p-CH3C6H4B(OH)2
(C6H5Se)2
(C6H5Se)2
(C6H5Se)2
(C6H5Se)2
(C6H5Se)2
(C6H5Se)2
(C6H5Se)2
(C6H5Se)2
(C6H5Se)2
(C6H5Se)2
(C6H5Te)2
(C6H5Te)2
(C6H5Te)2
(C6H5Te)2
(C6H5Te)2
(n-C4H9Se)2
(n-C4H9Se)2
2
C6H5B(OH)2
88
3
3
p-CH3OC6H4B(OH)2
o-CH3C6H4B(OH)2
p-ClC6H4B(OH)2
84
4
4
95
5
5
82
6
6
p-CH3COC6H4B(OH)2
a-C10H7B(OH)2
63
7
7
80
8
8
2,6-(CH3O)2C6H3B(OH)2
(E)-C6H5CH=CHB(OH)2
(E)-Cl(CH2)3CH=CHB(OH)2
p-CH3C6H4B(OH)2
p-CH3OC6H4B(OH)2
p-CH3COC6H4B(OH)2
2,6-(CH3O)2C6H3B(OH)2
p-ClC6H4B(OH)2
89
9
9
60
10
11
12
13
10
11
12
13
14
15
16
17
87
CuI (2.5 mol%)
CuI (1 mol%)
71c
80c
61c
81c
68c
62
None
a Reaction conditions: p-tolylboronic acid (1.00 mmol), diphenyl
diselenide (0.50 mmol), Cu salt (its amount indicated in Table 1) in
DMSO (3 mL) at 100 °C for 7 h.
b Isolated yields.
p-CH3OC6H4B(OH)2
p-CH3C6H4B(OH)2
In order to enhance the utility of the reaction, a variety of
substrates (diaryl diselenides and diphenyl ditelluride)
and organoboronic acids (aryl and vinyl) were evaluated.
The results are listed in Table 2. The data indicated that,
only in the presence of catalytic amount of cuprous iodide
and in DMSO at 100 °C, the reaction of boronic acids with
diaryl diselenides and diphenyl ditelluride went smoothly
to generate the corresponding products. Substituent ef-
fects were also screened. An electron-donating group on
the benzene ring of arylboronic acid enhanced the reaction
and led to the desired products in excellent yields (entries
1, 3, 4, 8, 11, 12 and 14). Strong electron-withdrawing
groups led to slower reaction and moderate yields of prod-
68
a Reaction conditions: organoboronic acid (1.00 mmol), diaryl
diselenide or ditelluride (0.50 mmol), CuI (0.10 mmol) in DMSO
(3 mL) at 100 °C for 7 h.
b Isolated yields.
c In the presence of N2.
As an alternative to organoboronic acids and esters, orga-
notrifluoroborate salts have emerged as a new class of air-
stable boron derivatives, facile to prepare in high yields
and purities, easy to handle, and feasible to utilize in a
number of useful synthetic processes.17 When the reaction
of potassium aryltrifluoroborates with diphenyl diselenide
Synlett 2005, No. 13, 2007–2010 © Thieme Stuttgart · New York

LETTER
Synthesis of Unsymmetrical Diaryl Selenides and Tellurides
2009
General Procedure for the Synthesis of Unsymmetrical Diaryl
Selenides and Tellurides in DMSO
and ditelluride was performed under the present reaction
conditions, as expected, good yields of the desired prod-
ucts were isolated (Scheme 2).
Organoboronic acid or potassium aryltrifluoroborate (1.00 mmol),
diphenyl diselenide or ditelluride (0.50 mmol), cuprous iodide (0.10
mmol) were added in a round-bottomed flask contained DMSO (3
mL). The resulting mixture was stirred at 100 °C for 7 h. After com-
pletion of the reaction, the mixture was vacuum filtered using a sin-
tered glass funnel and purified by flash chromatography to give the
desired products.
Ionic liquids, especially ambient-temperature ionic liq-
uids consisting of 1,3-dialkylimidazolium cations, have
shown great promise as alternating green solvents (reac-
tion medium) for organic transformations in recent years,
because of their non-volatile, chemically and thermally
stable, non-flammatory nature.15 However, there is only
one report on the stereospecific synthesis of vinyl
selenides through the reaction of vinylboronic acids and
vinylboronic esters with phenylselenyl chloride in
BmimBF4.16 When 1-n-butyl-3-methylimidazolium tetra-
fluoroborate (BmimBF4) was used as solvent instead of
DMSO for the reaction of p-methoxyphenylboronic acid
with diphenyl diselenide in the presence of CuI (10
mol%), only 16% yield of phenyl p-tolyl selenide was iso-
lated. In an effort to improve the yield of the reaction, we
next tried Cu(OAc)2 and CuSO4 as copper sources (better
Acknowledgment
We gratefully acknowledge financial support by the National Natu-
ral Science Foundation of China (No. 20372024), the Excellent Sci-
entist Foundation of Anhui Province, China (No. 04046080), the
Scientific Research Foundation for the Returned Overseas Chinese
Scholars, State Education Ministry, China (No. 2002247), the Ex-
cellent Young Teachers Program of MOE, China (No. 2024), and
the Key Project of Science and Technology of State Education
Ministry, China (No. 0204069).
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+
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R
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yield 92%
yield 78%
yield 82%
R = 2,6-(CH3O)2
R = 2,6-(CH3O)2
Scheme 2
In conclusion, we have developed a novel and high effi-
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selenides and tellurides in good to excellent yields
through the reaction of arylboronic acids, vinylboronic
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