Copper-catalyzed C-Se coupling of diphenyl diselenide with arylboronic acids at room temperature

Article abstract of DOI:10.1016/j.tet.2013.04.124

An efficient synthetic protocol for the Cu-catalyzed cross-coupling of diphenyl diselenide and arylboronic acid at room temperature was described. This catalytic system could tolerate a variety of arylboronic acids with only 3 mol % amount of CuSO₄ as the catalyst and inexpensive 1,10-phen. H ₂O as the ligand. Moreover, this catalytic system used environment-friendly EtOH as the solvent and catalytic amount of Na ₂CO₃ (20 mol %) as the base in the air.

Full text of DOI:10.1016/j.tet.2013.04.124

Tetrahedron 69 (2013) 5342e5347
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Copper-catalyzed CeSe coupling of diphenyl diselenide with
arylboronic acids at room temperature
*
Bo Zheng, Ying Gong, Hua-Jian Xu
School of Medical Engineering, Hefei University of Technology, Key Laboratory of Advanced Functional Materials and Devices, Hefei 230009,
Anhui Province, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient synthetic protocol for the Cu-catalyzed cross-coupling of diphenyl diselenide and arylboronic
acid at room temperature was described. This catalytic system could tolerate a variety of arylboronic
acids with only 3 mol % amount of CuSO4 as the catalyst and inexpensive 1,10-phen. H2O as the ligand.
Moreover, this catalytic system used environment-friendly EtOH as the solvent and catalytic amount of
Na2CO3 (20 mol %) as the base in the air.
Received 20 February 2013
Received in revised form 15 April 2013
Accepted 26 April 2013
Available online 6 May 2013
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
CeSe coupling
Copper-catalyzed
Diphenyl diselenide
Arylboronic acids
Room temperature
1. Introduction
scope of Cu and other transition-metal catalytic systems needed
high reaction temperature or aprotic solvent. So it is important that
Selenium is one of the essential trace elements, which has
a variety of immune and biological functions, especially in the
prevention of cardiovascular disease, anti-tumor, anti-viral dis-
eases, as well as anti-aging effect.1 In addition, many organo-
selenium compounds have been studied as catalysts and
intermediates in organic synthesis2 and material science.3 There-
fore, it is very significant to research on a variety of synthetic
methods for organoselenium. The traditional methods for the for-
mation of CeSe bond are associated with serious disadvantages
including: (i) the use of toxic solvents, such as hexamethyl phos-
phoric triamide (HMPA);4 (ii) harsh reaction conditions, such as
reaction of benzeneselenate anion and aryl halide in liquid am-
monia under UV light, etc.;5 (iii) expensive and toxic reagents.6 To
resolve these problems, many research groups have made great
effort to develop a number of synthesis methods in recent years.
Transition-metal-catalyzed methods played an important role in
CeSe bond formation. A variety of metals, including Ni,7 Pd,8 In,9,13
Zn10 Cu,11 and Fe14 catalyst systems have been studied for this
purpose. However, the application of Pd catalyst is restricted in
large-scale processes because of their high cost, air sensitivity and
of 10 tedious procedure for the preparation of ligands, and the
more mild (at room temperature), efficient, and environment-
friendly catalytic system need to be developed.
With the wide variety of commercially available and stable
boronic acids and derivatives, many studies have reported boronic
acids as reagents for the CeSe bond formation. In the past years,
the reactions of organoboronic acids with diselenides have been
reported. The first CeSe cross-coupling reaction of boronic acids
with diselenides was reported by Taniguchi12a using CuI as cata-
lyst at 100 ꢀC in DMSOeH2O mixed solvent (Scheme 1a). Later,
Wang et al. described that indium13 (Scheme 1b) or iron14
(Scheme 1c) catalyzed cross-coupling reactions of arylboronic
acids with diselenides employing DMSO as solvent at 130 ꢀC.
Alves et al. also reported the reaction of diaryl diselenides and
arylboronic acids, which used a recyclable catalyst15 (Scheme 1d)
or a recyclable solvent16 (Scheme 1e). Unfortunately, these re-
actions have some disadvantages, such as high reaction temper-
ature, harmful solvents, and long reaction time. Recently, our
group17 reported the oxidative cross-coupling reactions of diverse
boronic acids with thiols using CuSO4 as a simple and inexpensive
catalyst in ethyl alcohol at room temperature (Scheme 2). We
would like to develop a general protocol for the cross-coupling
reactions of diverse boronic acids with diphenyl diselenide with
a simple copper catalyst in an environment-friendly solvent at
room temperature.
* Corresponding author. Tel.: þ86 551 62904353; fax: þ86 551 62904405; e-mail
address: hjxu@hfut.edu.cn (H.-J. Xu).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.04.124

B. Zheng et al. / Tetrahedron 69 (2013) 5342e5347
5343
of product was obtained (Table 1, entry 1). Because nBu4NOH (40%
aq) is relativelyexpensiveand stronglyalkaline, we attempted touse
traditional inorganic bases, such as KOH, NaOH, Cs2CO3, Na2CO3
instead of nBu4NOH (40% aq) (Table 1, entries 2e5). To our delight,
the yield reached up to 98% when KOH (5% aq) (Table 1, entry 2) or
Na2CO3 (5% aq) (Table 1, entry 5) was used. We chose Na2CO3 as
a base in further examination. Then, we screened the concentration
of Na2CO3 and investigated the influence of the amount of Na2CO3
on this reaction (Table 1, entries 6e9). The results showed that
0.1 mL of 5% Na2CO3 (aq) was suitable for the desired conversion
(Table 1, entry 8). To make this reaction system simpler, we carried
out this reaction in the air, and the yield could reach 85% (Table 1,
entry 10). To our pleasure, a 99% yield was observed when the
amount of phenylboronic acid is increased to 1.1 equiv (with com-
parison of 0.5 equiv of diphenyl diselenide) (Table 1, entry 11). The
yield decreased sharply to 50% when the reaction time reduced to
3 h under air atmosphere (Table 1, entry 12). It could not provide
satisfactory results using water as a solvent instead of EtOH (Table 1,
entry 13). Considering the influence of catalyst, when we used other
copper salts as catalyst, the product yield could reach up to 75%e80%
(Table 1, entries 14 and 15). Only 17% product was observed when
the reaction was performed in the presence of FeCl3$3H2O (Table 1,
entry 16), and no product was obtained without the catalyst (Table 1,
entry 18). The control experiment showed that only a 25% yield of
product was observed in the absence of a ligand (Table 1, entry 19).
With the optimal condition in hand, we examined the isolated
yields for the reactions of a number of boronic acids and diphenyl
diselenide. The results are listed in Table 2. It was found that o-
methyl, m-methyl, p-methyl groups on the phenylboronic acids rings
were veryeffective in this process and gave the desired products over
93% yields (Table 2, entries 1bed). Furthermore, the bromo, chloro
groups did not interfere with the transformation, which made fur-
ther cross-coupling at the halogenated positions (Table 2, entries
1hej). Although the reaction yields of 4-bromophenylboronic acid
and 4-(trifluoromethyl)phenylboronic acid were a little low for 5 h,
they could reach up to 80% and 82% by increasing the reaction time,
respectively (Table 2, entries 1jek). More importantly, the coupling
of phenylboronic acid with diselenides in a 10 mmol (gram scale) also
(a)
(b)
(c)
(d)
(e)
Scheme 1. The reported reactions of boronic acids with diselenides.
Scheme 2. Our studies on the reactions of boronic acids with chalcogenide.
2. Results and discussion
The reaction of diphenyl diselenide and phenylboronic acid was
carried out as a model reaction (Table 1). According to our developed
method,17 the initial study was carried out using CuSO4 as a catalyst
and tetra-n-butylammonium hydroxide (nBu4NOH (40% aq)) as
a base in EtOH under O2 atmosphere at room temperature, 98% yield
Table 1
Optimization of the reaction conditionsa
Entry
Base
Catalyst (mol %)
Ligand (mol %)
Atmosphere
t (h)
Yieldb (%)
1
2
3
4
5
6
7
8
nBu4NOH (40% aq, 0.5 mL)
KOH (5% aq, 0.5 mL)
NaOH (5% aq, 0.5 mL)
Cs2CO3 (5% aq, 0.5 mL)
Na2CO3 (5% aq, 0.5 mL)
Na2CO3 (1% aq, 0.5 mL)
Na2CO3 (5% aq, 0.2 mL)
Na2CO3 (5% aq, 0.1 mL)
d
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
CuSO4 (3)
Cu(OAc)2 (3)
CuBr (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (3)
1,10-phen. H2O (1)
1,10-phen. H2O (3)
d
O2
O2
O2
O2
O2
O2
O2
O2
5
5
5
5
5
5
5
5
5
5
5
3
5
5
5
5
5
5
5
98
98
95
72
98
59
83
98
45
85
99
50
35c
80
75
17
43
Trace
25
9
O2
10
11d
12d
13d
14d
15d
16d
17d
18d
19d
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Na2CO3 (5% aq, 0.1 mL)
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
FeCl3$3H2O (3)
CuSO4 (1)
d
CuSO4 (3)
The highest yield is indicated in bold.
a
Unless otherwise noted, 0.2 mmol diphenyl diselenide, 0.4 mmol phenylboronic acid, 0.6 mL EtOH.
Yields determined by GC.
In 0.6 mL H2O.
b
c
d
0.44 mmol phenylboronic acid.

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B. Zheng et al. / Tetrahedron 69 (2013) 5342e5347
Table 2
The reactions of diphenyl diselenide with arylboronic acidsa,b
a Reactions were carried out using aryl or heteroaryl boronic acids (0.44 mmol), diphenyl diselenide (0.2 mmol) at room temperature under air atmosphere for 5
h. b Yields are given for isolated products and are calculated by the standard of diselenides. c 17 h. d 22 h. e Na2CO3 (5% aq., 1.0 mL), EtOH (1.0 mL).
could give 73% isolated yield, which made this protocol suitable for
industrial application. To our delight, 4-hydroxyphenolboronic acid
was also successfully coupled in good yield avoiding oxidative CeO
coupling (Table 2, entry 1q).
Carbonyl or ester group substituted arylboronic acids could not be
tolerated in our previous CeS coupling reaction,17 but they gave 90%
and 76% yield in this reaction system, respectively (Table 2, entries
1teu). The above results indicated that electron-withdrawing and
electron-donating arylboronic acids were not affected. Although the
reaction yields were influenced by sterically hindered ortho sub-
stituents, theycould still reach upto 55%e70% (Table 2, entries 1vew).
It is noteworthy that heteroaryl boronic acids also provided the cor-
responding products in good yields (Table 2, entries 1xez), especially
2-fluoropyridine-5-boronic acid could give a 93% yield (Table 2, entry
1x). However, 2-thiophene boronic acid and n-butyl boronic acid
could not react in current protocol (Table 2, entries 1aaeab).
According to the previous studies12,17 and the above experi-
mental results, we propose the mechanism as follows (Scheme 3).
Scheme 3. Proposed mechanism.
Initially, Cu (II) intermediate a is quickly formed by CuSO4 and 1,10-
phen. H2O. Then, intermediate b is formed from diphenyl dis-
elenide with Cu (II) intermediate a via an oxidative addition,
ArB(OH)2 reacts with b via transmetallation to form intermediate c
and [PhSe]ꢁ, which is then oxidized by O2 to regenerate [PhSe]2.
Sequentially, reductive elimination ensues to form the product
Scheme 4. The reaction of diphenyl diselenide and phenylboronic acid under argon.
PhSeAr and Cu (II) intermediate a to complete the catalytic cycle.
This reaction may occur under Ar atmosphere and only a 47% yield
of product was obtained (Scheme 4).
under mild reaction conditions. This method has the following
advantages: (i) at room temperature; (ii) the use of environment-
3. Conclusion
friendly EtOH as solvent; (iii) under air atmosphere; (iv) only
3 mol % CuSO4 as catalyst. Due to the convenient operation and
environmental friendliness of this procedure, we hope the de-
veloped catalytic method can be applied not only in laboratory but
also in large-scale production.
In conclusion, we developed a simple, efficient, economical, and
environmentally friendly protocol for the synthesis of diaryl sele-
nides by coupling of arylboronic acid with diphenyl diselenide

B. Zheng et al. / Tetrahedron 69 (2013) 5342e5347
5345
4. Experimental section
J¼7.4 Hz, 1H), 2.40 (s, 3H). 13C NMR (151 MHz, CDCl3):
d
139.9, 133.7,
132.8, 131.7, 130.8, 130.2, 129.4, 127.9, 127.2, 126.7, 22.4.
4.1. General procedures for the optimization of the reaction
condition
4.2.5. 4-Methoxyphenyl-phenyl-selenide (1e).13 The reaction of 5 h,
purification by column chromatography (petroleum ether), a pale
yellow liquid (89 mg, 85% yield). 1H NMR (600 MHz, CDCl3):
d 7.50
4.1.1. General procedure A. Diphenyl diselenide (0.2 mmol), phe-
nylboronic acid (0.4 mmol), CuSO4 (3 mol %), 1,10-phen. H2O
(3 mol %) were thrown into 25 mL oven-dried Schlenk tube. The
tube was evacuated and filled with oxygen (this procedure was
repeated three times). Then solvent (0.6 mL) was added with a sy-
ringe under a counter flow of oxygen. After 1 min, base (0.1e0.5 mL)
was added with a syringe under a counter flow of oxygen and the
mixture stirred vigorously at room temperature for 5 h. The re-
action mixture was then diluted with Et2O, filtered, washed with
copious washings (Et2O), biphenyl (0.4 mmol) was added as in-
ternal standard. The yield was determined by GC.
(d, J¼8.7 Hz, 2H), 7.32 (d, J¼7.1 Hz, 2H), 7.23e7.14 (m, 3H), 6.85 (d,
J¼8.7 Hz, 2H), 3.80 (s, 3H). 13C NMR (151 MHz, CDCl3):
d 159.8,
136.5, 133.2, 130.9, 129.1, 126.4, 119.9, 115.1, 55.3.
4.2.6. 4-Methylthiophenyl-phenyl-selenide (1f).13 The reaction of 5 h,
purification by column chromatography (petroleum ether), a pale
yellow liquid (78 mg, 70% yield). 1H NMR (600 MHz, CDCl3):
d 7.41 (m,
4H), 7.25 (m, 3H), 7.16 (d, J¼8.3Hz, 2H), 2.46 (s, 3H).13C NMR (151 MHz,
CDCl3): d 138.4, 134.1, 132.3, 131.7, 129.3, 127.2, 127.1, 126.7, 15.7.
4.2.7. 4-Fluorophenyl-phenyl-selenide (1g).11j The reaction of 5 h,
purification by column chromatography (petroleum ether), a pale
yellow liquid (92 mg, 92% yield). 1H NMR (600 MHz, CDCl3):
d 7.49
4.1.2. General procedure B. Diphenyl diselenide (0.2 mmol), phe-
nylboronic acid (0.4 mmol or 0.44 mmol), Cu or Fe sources
(1e3 mol %), 1,10-phen. H2O (1e3 mol %) were thrown into 25 mL
oven-dried Schlenk tube. Then solvent (0.6 mL) was added with
a syringe. After 1 min, Na2CO3 (5% aq, 0.1 mL) was added with
a syringe and the mixture stirred vigorously at room temperature
for 3 h or 5 h. The reaction mixture was then diluted with Et2O,
filtered, washed with copious washings (Et2O), biphenyl (0.4 mmol)
was added as internal standard. The yield was determined by GC.
(dd, J¼8.4, 5.5 Hz, 2H), 7.41 (m, 2H), 7.29e7.22 (m, 3H), 6.99 (t,
J¼8.6 Hz, 2H). 13C NMR (151 MHz, CDCl3):
d 163.4, 161.7, 135.7, 135.7,
132.2, 131.7, 129.3, 127.2, 125.2, 116.6, 116.5.
4.2.8. 3-Chlorophenyl-phenyl-selenide (1h).11b The reaction of 5 h,
purification by column chromatography (petroleum ether), a col-
orless oil (95 mg, 89% yield). 1H NMR (600 MHz, CDCl3):
d
7.54e7.49
(m, 2H), 7.40 (s,1H), 7.30 (m, 4H), 7.21 (m,1H), 7.17 (m,1H). 13C NMR
(151 MHz, CDCl3):
129.5, 128.0, 127.2.
d 134.9, 133.9, 133.5, 131.7, 130.2, 130.1, 129.8,
4.2.9. 4-Chlorophenyl-phenyl-selenide (1i).15 The reaction of 5 h,
purification by column chromatography (petroleum ether), a col-
4.2. Experimental procedures for the reaction of boronic
acids and diphenyl diselenide
orless oil (91 mg, 85% yield). 1H NMR (600 MHz, CDCl3):
d
7.46 (m,
2H), 7.37 (m, 2H), 7.30e7.26 (m, 3H), 7.23 (m, 2H). 13C NMR
(151 MHz, CDCl3): 134.1, 133.5, 133.2, 130.6, 129.5, 129.4, 127.6.
Diphenyl diselenide (0.2 mmol), boronic acid (0.44 mmol),
CuSO4 (3 mol %, 20 mg), 1,10-phen. H2O (3 mol %, 24 mg) were
thrown into 25 mL oven-dried Schlenk tube. Then, EtOH (0.6 mL)
was added with a syringe. After 1 min, Na2CO3 (5% aq) (0.1 mL or
1 mL) was added and the mixture stirred vigorously at room tem-
perature for 5 he22 h. After completion of the reaction, the reaction
mixture was diluted with Et2O, filtered, washed with copious
washings (Et2O or EtOAc), concentrated. The crude product was
purified on a short silica gel column (ethyl acetate or petroleum
ether).
d
4.2.10. 4-Bromophenyl-phenyl-selenide (1j).15 The reaction of 17 h,
purification by column chromatography (petroleum ether), a white
solid (100 mg, 80% yield), mp: 33.7e35.0 ꢀC. 1H NMR (600 MHz,
CDCl3):
CDCl3):
d
7.47 (m, 2H), 7.38 (m, 2H), 7.30 (m, 5H). 13C NMR (151 MHz,
134.2, 133.3, 132.4, 130.4, 130.4, 129.5, 127.7, 121.5.
d
4.2.11. 4-(Trifluoromethyl)phenyl-phenyl-selenide (1k).11f The re-
action of 22 h, purification by column chromatography (petroleum
ether), a colorless oil (99 mg, 82% yield). 1H NMR (600 MHz, CDCl3):
4.2.1. Diphenyl-selenide (1a).15 The reaction of 5 h, purification by
d
7.51 (m, 2H), 7.46 (d, J¼8.6 Hz, 2H), 7.34e7.28 (m, 3H), 7.12 (d,
column chromatography (petroleum ether), a colorless oil (86 mg,
J¼8.6 Hz, 2H). 13C NMR (151 MHz, CDCl3):
d 148.5, 148.5, 133.9,
92% yield). 1H NMR (600 MHz, CDCl3):
d
7.48 (m, 4H), 7.28 (m, 6H).
13C NMR (151 MHz, CDCl3):
d 133.0, 131.1, 129.3, 127.3.
133.5, 130.3, 129.9, 129.5, 127.8, 121.8, 121.3, 119.5.
4.2.12. 4-(Phenyl)phenyl-phenyl-selenide (1l).18 The reaction of 5 h,
purification by column chromatography (petroleum ether), a light
yellow solid (93 mg, 75% yield), mp: 71.3e72.2 ꢀC. 1H NMR
4.2.2. 3-Tolyl-phenyl-selenid (1b).11b The reaction of 5 h, purifica-
tion by column chromatography (petroleum ether), a pale yellow
liquid (94 mg, 95% yield). 1H NMR (600 MHz, CDCl3):
d 7.49e7.44
(600 MHz, CDCl3):
d
7.56 (d, J¼7.7 Hz, 2H), 7.51 (m, 6H), 7.43 (t,
(m, 2H), 7.33 (s, 1H), 7.27 (m, 4H), 7.17 (t, J¼7.6 Hz, 1H), 7.09 (d,
J¼7.7 Hz, 2H), 7.34 (t, J¼7.4 Hz, 1H), 7.32e7.26 (m, 3H). 13C NMR
J¼7.6 Hz, 1H), 2.31 (s, 3H). 13C NMR (151 MHz, CDCl3):
d 139.2, 133.8,
(151 MHz, CDCl3):
d 140.4, 140.3, 133.3, 133.1, 131.1, 130.2, 129.4,
132.8, 131.4, 130.7, 130.3, 129.3, 129.3, 128.3, 127.2, 21.3.
128.8, 128.0, 127.5, 127.4, 127.0.
4.2.3. 4-Tolyl-phenyl-selenide (1c).11b The reaction of 5 h, purifica-
4.2.13. 3-(Trifluoromethoxy)phenyl-phenyl-selenide (1m). The re-
action of 5 h, purification by column chromatography (petroleum
ether), a colorless oil (124 mg, 98% yield). 1H NMR (600 MHz,
tion by column chromatography (petroleum ether), a yellow liquid
(93 mg, 94% yield). 1H NMR (600 MHz, CDCl3):
d 7.51e7.37 (m, 4H),
7.29e7.20 (m, 4H), 7.12 (d, J¼7.9 Hz, 2H), 2.35 (s, 3H). 13C NMR
CDCl3):
d 7.53 (m, 2H), 7.31 (m, 4H), 7.26e7.22 (m, 2H), 7.07 (d,
(151 MHz, CDCl3):
126.9, 21.2.
d 137.7, 133.9, 132.0, 131.5, 130.2, 129.2, 127.7,
J¼8.1 Hz, 1H). 13C NMR (151 MHz, CDCl3):
d 149.5, 134.2, 133.9,
130.2, 129.9, 129.6, 129.3, 128.2, 124.0, 121.2, 119.5, 119.2. HRMS
calcd for C13H9F3OSe (Mþ): 317.9771; found: 317.9774.
4.2.4. 2-Tolyl-phenyl-selenide (1d).15 The reaction of 5 h, purifica-
tion by column chromatography (petroleum ether), a pale yellow
4.2.14. 4-Cyanophenyl-phenyl-selenide (1n).14b The reaction of 5 h,
purification by column chromatography (petroleum ether/ethyl
liquid (92 mg, 93% yield). 1H NMR (600 MHz, CDCl3):
d
7.40 (dd,
J¼6.4, 3.2 Hz, 2H), 7.34 (d, J¼7.7 Hz, 1H), 7.30e7.17 (m, 5H), 7.07 (t,

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B. Zheng et al. / Tetrahedron 69 (2013) 5342e5347
acetate¼50:1), a colorless oil (88 mg, 85% yield). 1H NMR (600 MHz,
a colorless oil (60 mg, 55% yield). 1H NMR (600 MHz, CDCl3):
d 7.58
CDCl3):
d
7.60 (m, 2H), 7.46e7.36 (m, 5H), 7.32 (d, J¼8.4 Hz, 2H). 13
C
(dd, J¼7.5, 1.8 Hz, 2H), 7.33 (m, 3H), 7.18 (t, J¼7.7 Hz, 1H), 6.95 (dd,
NMR (151 MHz, CDCl3):
127.4, 118.8, 109.5.
d 141.0, 135.7, 132.4, 130.2, 129.9, 129.2,
J¼7.7, 1.5 Hz, 1H), 6.85 (d, J¼8.1 Hz, 1H), 6.78 (t, J¼7.2 Hz, 1H), 3.88
(s, 3H). 13C NMR (151 MHz, CDCl3):
d 156.6,135.4,130.8,129.4, 128.3,
128.1, 127.7, 121.9, 121.6, 110.4, 55.9.
4.2.15. 3-Cyanophenyl-phenyl-selenide (1o).18 The reaction of 5 h,
purification by column chromatography (petroleum ether/ethyl
acetate¼50:1), a colorless oil (83 mg, 80% yield). 1H NMR (600 MHz,
4.2.24. 4-Fluoro-5-(phenylselanyl)pyridine (1x). The reaction of 5 h,
purification by column chromatography (petroleum ether/ethyl
acetate¼50:1), a pale yellow liquid (94 mg, 93% yield). 1H NMR
CDCl3):
d
7.58 (m, 2H), 7.55 (m, 2H), 7.48 (d, J¼7.6 Hz, 1H), 7.40e7.28
(m, 4H). 13C NMR (151 MHz, CDCl3):
d
135.4, 134.7, 134.4, 134.2,
(600 MHz, CDCl3):
d
8.32 (m, 1H), 7.86 (ddd, J¼8.4, 7.7, 2.4 Hz, 1H),
7.44 (m, 2H), 7.28 (m, 3H), 6.86 (dd, J¼8.4, 2.9 Hz, 1H). 13C NMR
130.2, 129.9, 129.6, 128.8, 128.4, 118.2, 113.4.
(151 MHz, CDCl3):
d 164.0, 162.4, 151.5, 151.4, 146.2, 146.1, 132.8,
4.2.16. (4-(Phenylselanyl)phenyl)methanol (1p). The reaction of 5 h,
purification by column chromatography (petroleum ether/ethyl
acetate¼5:1), an orange solid (95 mg, 90% yield), mp: 49.7e51.4 ꢀC.
130.1, 129.6, 127.9, 124.6, 124.6, 110.7, 110.5. HRMS calcd for
C11H8FNSe (Mþ): 252.9806; found: 252.9803.
1H NMR (600 MHz, CDCl3):
d 7.48e7.43 (m, 4H), 7.26 (m, 5H), 4.66
4.2.25. 2-Phenylselenyl-furan (1y).11b The reaction of 5 h, purifica-
(s, 2H), 1.75 (s, 1H). 13C NMR (151 MHz, CDCl3):
d 140.1, 133.3, 132.8,
tion by column chromatography (petroleum ether), a yellow oil
131.1, 130.2, 129.3, 127.9, 127.3, 64.8. HRMS calcd for C13H12OSe
(54 mg, 60% yield). 1H NMR (600 MHz, CDCl3):
d 7.59 (m, 1H), 7.34
(Mþ): 264.0053; found: 264.0055.
(m, 2H), 7.27e7.19 (m, 3H), 6.76 (dd, J¼3.2, 0.7 Hz, 1H), 6.45 (dd,
J¼3.2, 1.9 Hz, 1H). 13C NMR (151 MHz, CDCl3):
d 147.1, 138.2, 131.6,
4.2.17. 4-Hydroxylphenyl-phenyl-selenide (1q).8 The reaction of 5 h,
purification by column chromatography (petroleum ether/ethyl
acetate¼20:1), a brown liquid (70 mg, 70% yield).1H NMR (600 MHz,
130.3, 129.3, 126.90, 120.8, 111.9.
4.2.26. 2-(Phenylselanyl)benzofuran (1z). The reaction of 5 h, puri-
fication by column chromatography (petroleum ether), a light
yellow solid (66 mg, 60% yield), mp: 39.6e40.6 ꢀC. 1H NMR
CDCl3):
d
7.46 (d, J¼8.7 Hz, 2H), 7.36e7.32 (m, 2H), 7.27e7.17 (m, 3H),
6.79 (d, J¼8.7 Hz, 2H), 5.38 (s, 1H). 13C NMR (151 MHz, CDCl3):
d
155.8, 136.72, 133.0, 131.0, 129.2, 126.5, 120.1, 116.6.
(600 MHz, CDCl3):
d
7.55 (d, J¼7.8 Hz, 1H), 7.47 (d, J¼5.5 Hz, 3H),
7.30e7.20 (m, 7H), 7.03 (s, 1H). 13C NMR (151 MHz, CDCl3):
d
157.5,
4.2.18. 4-Ethoxyphenyl-phenyl-selenide (1r). The reaction of 5 h,
purification by column chromatography (petroleum ether), a yel-
143.6,131.6,129.9,129.4,128.5,127.5,124.8,123.0,120.7,115.9,111.3.
HRMS calcd for C14H10OSe (Mþ): 273.9897; found: 273.9899.
low liquid (78 mg, 70% yield). 1H NMR (600 MHz, CDCl3):
d 7.49 (d,
J¼8.6 Hz, 2H), 7.32 (d, J¼7.3 Hz, 2H), 7.19 (m, 3H), 6.84 (d, J¼8.7 Hz,
2H), 4.02 (q, J¼7.0 Hz, 2H), 1.41 (t, J¼7.0 Hz, 3H). 13C NMR (151 MHz,
Acknowledgements
CDCl3):
d 159.2, 136.6, 133.3, 130.8, 129.1, 126.4, 119.7, 115.6, 63.5,
14.8. HRMS calcd for C14H14OSe (Mþ): 278.0210; found: 278.0207.
We gratefully acknowledge financial support from the National
Natural Science Foundation of China (No. 21272050, 21072040,
21071040) and the Program for New Century Excellent Talents in
University of the Chinese Ministry of Education (NCET-11-0627).
4.2.19. 2-Naphthyl-phenyl-selenide (1s).16 The reaction of 5 h, puri-
fication by column chromatography (petroleum ether), a light yellow
solid (85 mg, 75% yield), mp: 55.2e56.4 ꢀC. 1H NMR (600 MHz,
CDCl3):
d
7.99 (s, 1H), 7.81 (m, 1H), 7.73 (m, 2H), 7.50 (m, 5H),
134.0, 132.9, 132.4,
7.30e7.26 (m, 3H). 13C NMR (151 MHz, CDCl3):
d
Supplementary data
132.1, 131.2, 130.5, 129.4, 128.8, 128.4, 127.8, 127.4, 127.3, 126.5, 126.2.
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2013.04.124.
These data include MOL files and InChiKeys of the most important
compounds described in this article.
4.2.20. 1-(4-(Phenylselanyl)phenyl)ethanone (1t).15 The reaction of
5 h, purification by column chromatography (petroleum ether/ethyl
acetate¼20:1), a colorless liquid (99 mg, 90% yield). 1H NMR
(600 MHz, CDCl3):
d
8.02 (t, J¼1.7 Hz, 1H), 7.84e7.79 (m, 1H),
7.61e7.56 (m, 1H), 7.50 (m, 2H), 7.34 (t, J¼7.8 Hz, 1H), 7.31e7.26 (m,
References and notes
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