Synthesis of Unsymmetrical Diaryl Selenides: Copper-Catalyzed Se-Arylation of Diaryl Diselenides with Triarylbismuthanes

Article abstract of DOI:10.1055/s-0035-1561280

Copper-catalyzed C(aryl)-Se bond formation by the reaction of diaryl diselenides with triarylbismuthanes in the presence of copper(I) acetate (10 mol%) and 1,10-phenanthroline (10 mol%) under aerobic conditions led to the formation of unsymmetric diaryl s

Full text of DOI:10.1055/s-0035-1561280

SYNTHESIS
0
0
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8
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1
1
4
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0
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©
Georg Thieme Verlag Stuttgart · New York
2016, 48, 730–736
730
paper
Synthesis
M. Matsumura et al.
Paper
Synthesis of Unsymmetrical Diaryl Selenides: Copper-Catalyzed
Se-Arylation of Diaryl Diselenides with Triarylbismuthanes
Mio Matsumuraa
Kohki Shibataa
Sota Ozekia
Mizuki Yamadaa
Yuki Murataa
Cu(OAc) (10 mol%)
1,10-phen (10 mol%)
Ar1
Ar1 Bi
Ar2Se SeAr2
Se
+
Ar1
Ar2
Ar1
DMSO, 100 °C, air
28 examples
up to 91% yield
Naoki Kakusawab
Shuji Yasuike*a
a
School of Pharmaceutical Sciences, Aichi Gakuin University,
1
-100 Kusumoto-cho, Chikusa-ku, Nagoya 464-8650, Japan
b
Faculty of Pharmaceutical Sciences, Hokuriku University,
Ho-3 Kanagawa-machi, Kanazawa 920-1181, Japan
s-yasuik@dpc.agu.ac.jp
Received: 19.10.2015
Accepted after revision: 11.11.2015
Published online: 29.12.2015
nides) as sources of selenium for the synthesis of unsym-
metrical diaryl selenides, with respect to their odor,
stability, and toxicity. However, diphenyl diselenide is the
principal reagent used in this type of reaction; only a few
examples involving the use of other substituted diselenides
are known.
DOI: 10.1055/s-0035-1561280; Art ID: ss-2015-f0604-op
Abstract Copper-catalyzed C(aryl)–Se bond formation by the reaction
of diaryl diselenides with triarylbismuthanes in the presence of cop-
per(I) acetate (10 mol%) and 1,10-phenanthroline (10 mol%) under aer-
obic conditions led to the formation of unsymmetric diaryl selenides in
moderate to excellent yields. This reaction proceeded efficiently; all
three aryl groups in the bismuthane and both the selanyl groups in the
diaryl diselenide were transferred to the coupling products.
Organobismuth compounds are generally nontoxic, en-
10
vironmentally benign, and useful synthetic reagents. Tri-
valent organobismuth compounds such as triarylbis-
muthanes (Ar Bi) have been used as arylating agents in cop-
3
per-mediated N- and O-arylation reactions, even though
Key words bismuthanes, diselenides, selenides, copper, catalysis,
cross-coupling
stoichiometric amounts of the copper reagents were re-
quired.1
1,12
Moreover, triarylbismuthanes can also be used
for C(aryl)–Se bond-formation reactions. Diaryl selenides
were obtained by the reaction of diaryl diselenides with tri-
arylbismuthanes on heating to a high temperature (140 °C)
Recently, organoselenium compounds have attracted
interest because of their use as important reagents in or-
ganic synthesis and their potential biological activities.1
Among the various organoselenium compounds, diaryl sel-
enides have been prominent in the last two decades owing
to their wide range of biological and pharmaceutical prop-
erties, such as anticancer, antitumor, antiviral, antimicrobi-
,2
13
for a prolonged reaction time (24–48 h). Photoinduced re-
actions of diaryl diselenides with triarylbismuthanes also
afforded diaryl selenides; however, an excess of the bis-
muth agent bearing three aryl groups was required for this
reaction.14 We recently reported that a copper-catalyzed
C(aryl)–S bond-formation reaction of diaryl disulfides with
triarylbismuthanes can be conducted under aerobic condi-
tions.15 All three aryl groups of the bismuth reagent and
both the sulfanyl groups of the diaryl disulfide participated
in this reaction. As a continuation of our studies on C(aryl)–
heteroatom bond formation, we now report an atom-eco-
nomic and simple copper-catalyzed method for the synthe-
sis of diaryl selenides from diaryl diselenides and triarylbis-
muthanes in the absence of additives under aerobic condi-
tions.
3
al, and antioxidant activities. Consequently, many methods
have been developed for the synthesis of unsymmetrical di-
aryl selenides. Transition-metal-catalyzed C–Se bond for-
mation is one of the most popular methods for the synthe-
1c,4
sis of organoselenides.
Many studies have reported on
copper-catalyzed Se-arylation reactions. Such reactions are
generally conducted by reactions of aryl halides with sele-
5
6
7
nols, diselenides, or alkyltin selenides, reactions of aryl
4
c,8
9
boronic acids with diselenides or selenium bromides, or
reactions of arylsilanes or stannanes with selenium bro-
mides. However, except for the reactions of boronic acids
9
We previously reported that the cross-coupling reaction
of diaryl disulfides with triarylbismuthanes in the presence
of copper(I) acetate and 1,10-phenanthroline (1,10-phen)
as the catalytic system under aerobic conditions in dimeth-
with diselenides, most of these reactions require a base
and/or an inorganic reagent as an additive. In these reac-
tions, diaryl diselenides are superior to other selenium re-
agents (selenols, arylselenium bromides, or alkyltin sele-
15
yl sulfoxide afforded the corresponding diaryl sulfides. To
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Synthesis
M. Matsumura et al.
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evaluate the efficiency of triarylbismuthanes as aryl do-
nors, we examined the reaction between di-4-tolyl disele-
nide (12a) and the phenyl-substituted compounds 1–11,
which contain group 14, 15 or 16 elements, under the opti-
mal conditions determined previously [CuOAc (10 mol%),
Table 1 Copper-Catalyzed Coupling of Di-4-tolyl Diselenide with
Group 14, 15 or 16 Reagents
CuOAc (10 mol%)
,10-phen (10 mol%)
1
Se
PhnM
–11
+
(4-TolSe)2
Ph
4-Tol
DMSO, air
1
12a
13
1,10-phenanthroline (10 mol%), DMSO, 100 °C]. The prog-
ress of the reaction was monitored by gas–liquid chroma-
tography, and the reaction times necessary to obtain prod-
ucts 13 were determined (Table 1). In the case of group 14
compounds, tetraphenyllead (4, M = Pb) afforded com-
pound 13 in a moderate yield (60%) after a long reaction
time (24 h) (Table 1, entry 4). Among the pnictogen com-
pounds, triphenylbismuthane (8a, M = Bi) was efficiently
converted into 13; however, 5 (M = P), 6 (M = As), and 7
a
Entry
1b
Ph
n
M
Temp (°C)
Time (h)
Yield (%)
1
Ph
4
Si
100
100
100
100
100
100
100
100
100
100
100
60
24
24
24
24
24
24
24
2
7
10
21
60
8
b
2
2
Ph Ge
4
3b
3
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
4
4
3
3
3
3
2
2
2
3
Sn
Pb
P
4b
5c
6c
4
5
6
As
Sb
Bi
6
(M = Sb) showed no ability to transform (entries 5–8). The
chalcogen compounds 9–11 provided inferior results (en-
tries 9–11). These results show that triphenylbismuthane
7c
7
15
87
5
8c
8a
9
(
8a) is superior to other reagents for this Se-arylation in
9d
S
24
24
24
24
24
24
terms of the reaction time (2 h) and the yield of 13 (87%;
entry 8). Notably, all three phenyl groups of the bismuth re-
agent and both the selanyl groups of the diselenide partici-
pated in the reaction. When the reaction was carried out at
1
0d
1d
2c
10
11
8a
Se
Te
Bi
6
1
1
14
52
69
29
13c,e
8a
8a
Ph Bi
100
100
60 °C, compound 13 was obtained in 52% yield after 24
3
hours (entry 12). This shows that is necessary to heat the
reaction mixture at 100 °C to complete the reaction. De-
creasing the loading of copper(I) acetate from 10 mol% to 5
mol% or 1 mol% gave significantly lower yields of 13 (en-
tries 13 and 14). Screening of solvents showed that the best
results were obtained in dimethyl sulfoxide (2 h, 87%), al-
though the reaction proceed effectively in N,N-dimethyl-
formamide (80%) or N-methylpyrrolidin-2-one (71%) after
4c,f
1
3
Ph Bi
a
Yield by GLC. A 100% yield corresponds to the formation of 1 mmol (en-
tries 1–4), 1.5 mmol (entries 5–8, 12), or 1 mmol (entries 9–11) of 13.
b
1
–4 (0.25 mmol), 12 (0.5 mmol).
c
d
e
f
5
9
–8 (0.5 mmol), 12 (0.75 mmol).
–11 (0.5 mmol), 12 (0.5 mol).
CuOAc (5 mol%), 1,10-phenanthroline (5 mol%).
CuOAc (1 mol%), 1,10-phenanthroline (1 mol%).
24 hours, whereas acetonitrile (39%), toluene (9%), 1,4-di-
oxane (7%), and 1,2-dichloroethane (7%) gave inferior re-
sults.
11–20). Furthermore, this reaction gave the polysubstituted
diaryl selenides 23–26 by using various combinations of 8
and 12 (entries 21–26). All three aryl groups on the bis-
muth reagent and both the selanyl groups of the diselenide
participated in these Se-arylations. Moreover, the electronic
nature (electron-rich or electron-deficient) of the substitu-
ents in the 4-substituted series of bismuth and selenium re-
agents did not affect the outcome of this reaction (entries
1–5, 11–15, and 21–26). Additionally, the effect of steric
hindrance in the bismuth and selenium reagents was re-
markable: the bulkiest mesityl derivatives 8h and 12g were
superior reagents for this reaction in terms of their reaction
times and the yields of the Se-arylation products (entries 7,
17, 27, and 28). However, the reactions of triphenylbis-
muthane with dialkyl diselenides such as dibenzyl or dibu-
tyl diselenide resulted in complex mixtures, and did not af-
ford the desired coupling products.
To demonstrate the efficiency and generality of this Se-
arylation, we examined the reactions of various triarylbis-
muthanes (8; 0.75 mmol) and diaryl diselenides (12; 0.5
mmol) with copper(I) acetate (10 mol%) and 1,10-phenan-
throline (10 mol%) as the catalytic system under aerobic
conditions in dimethyl sulfoxide at 100 °C. The results are
summarized in Table 2. The reactions of triphenylbis-
muthane (8a) with diaryl diselenides 12a–e containing
electron-donating or electron-withdrawing groups on the
phenyl ring afforded the corresponding coupling products
13–17 in good to excellent yields (entries 1–5). The cou-
pling of the sterically hindered ortho-substituted disele-
nides 12f–h with 8a gave the corresponding selenides 18–
20 without any difficulty (entries 6–8). Moreover, the reac-
tions of the heterocyclic diselenides 12i and 12j afforded
the corresponding diaryl selenides 21 and 22 (entries 9 and
We also examined the reaction between di-4-tolyl ditel-
luride (27) with triphenylbismuthane (8a) under the same
conditions (Scheme 1). This gave the unsymmetrical diaryl
telluride 28 as the main product, along with the two sym-
metrical diaryl tellurides 29 and 30. The yields are based on
GLC analysis, because products 28–30 could not be separat-
10). Next, we treated various triarylbismuthanes 8b–k with
diphenyl diselenide (12k) under the same reaction condi-
tions. These reactions also afforded the corresponding cou-
pling products 13–22 in good to excellent yields (entries
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Synthesis
M. Matsumura et al.
Paper
ed by column chromatography on silica gel. Unfortunately,
this result shows that the reaction of di-4-tolyl ditelluride
(27) with triphenylbismuthane (8a) is ineffective for Te-
arylation.
At present, the mechanism of the Se-arylation reaction
is unclear. Scheme 2 shows a possible mechanism for the
synthesis of diaryl selenides through C(Ar)–Se bond forma-
tion from triarylbismuthanes and diaryl diselenides in the
presence of catalytic amounts of the copper(I) reagent. The
Ph3Bi
CuOAc
,10-phen
8a
1
Te
Te
Te
+
+
+
Ph
4-Tol Ph
Ph 4-Tol
4-Tol
DMSO, air
2
8: 66% 29: 5%
30: 20%
(
4-TolTe)2
27
Scheme 1 Copper-catalyzed Te-Arylation of di-4-tolyl ditelluride with
triphenylbismuthane
Table 2 Copper-Catalyzed Se-Arylation of Diaryl Diselenides with Triarylbismuthanesa
CuOAc (10 mol%)
1,10-phen (10 mol%)
Ar1
Se
Ar1 Bi
+
3/2
2
Ar Se SeAr2
Ar1
Ar2
Ar1
DMSO, 100 °C, air
8
12
13–26
Ar1
(Ar Se)
2
Ar2
Time (h)
b
Product
Yield (%)
c
Entry
Ar
3
Bi
2
1
2
3
4
5
6
7
8
9
8a
8a
8a
8a
8a
8a
8a
8a
8a
8a
8b
8c
8d
8e
8f
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
12b
12a
12c
12d
12e
12f
4-MeOC
4-Tol
6
H
4
2
14
13
15
16
17
18
19
20
21
22
14
13
15
16
17
18
19
20
21
22
23
23
24
24
25
25
26
26
80
87
85
78
89
88
82
90
82
85
83
86
86
81
85
84
86
85
72
74
85
82
91
90
88
85
84
85
2
4-ClC
4-EtO
4-F CC
6
H
4
1
2
CC
6
H
4
1.5
1
3
6 4
H
2-Tol
Mes
2
12g
12h
12i
2
1-naphthyl
2-thienyl
2
2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
12j
2-benzo[b]thienyl
2
4-MeOC
4-Tol
6
H
4
12k
12k
12k
12k
12k
12k
12k
12k
12k
12k
12a
12b
12e
12d
12e
12b
12g
12f
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
4-Tol
1.5
1.5
1
4-ClC
4-EtO
4-F CC
6 4
H
2
CC
6
H
4
1
3
6
H
4
1
8g
8h
8i
2-Tol
Mes
1.5
1
1-naphthyl
2-thienyl
1
8j
1
8k
8b
8c
8e
8f
2-benzo[b]thienyl
1.5
2
4-MeOC
4-Tol
6
H
4
4-MeOC
4-F CC
4-EtO
4-F CC
6
H
4
3
4-EtO
4-F CC
4-MeOC
4-F CC
2
CC
6
H
4
3
6
H
4
1.5
1.5
1.5
2
3
6
H
4
2
CC
6
H
4
8b
8f
6
H
4
3
6 4
H
3
6
H
4
4-MeOC
Mes
6 4
H
8g
8h
2-Tol
Mes
2
2-Tol
1
a
b
c
Reaction conditions: 8 (0.5 mmol), 12 (0.75 mmol), CuOAc (0.05 mmol), 1,10-phenanthroline (0.05 mmol), DMSO, 100 °C, air.
Heating was continued until the spot for the bismuth reagent on a TLC plate disappeared.
Isolated yield.
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Synthesis
M. Matsumura et al.
Paper
1
2
1
2
Ar SeAr
Ar SeAr
SeAr2
Ar1
SeAr2
Ar1
(
Cu
III)
(
Cu
III)
N
N
N
N
N
N
X
N
N
Cu
(I)
Cu
X
(
I)
X
X
E
A
E
O2 + H2O
cycle A
cycle B
Bi2O3
2
2
Ar13Bi + O2
SeAr2
Ar Se
Ar Se SeAr
1
2
Ar 3Bi
H
O
Ar1
SeAr2
N
N
N
N
Cu
Cu
Cu
X2
Cu
N (II) X
N (II) O (II) N
N (II) X
H
B
Bi2O3
O2 + H2O
D
C
Scheme 2 Possible mechanisms
catalytic cycle of this reaction should be similar to that of
μA). Elemental analysis was performed on MT-6 elemental analyzer
Yanagimoto). IR spectra were recorded on an FTIR-8400S system
(Shimadzu); only selected IR bands are reported. All chromatographic
separations were performed on Silica Gel 60N (Kanto Chemical Co.,
Inc.). TLC was performed with Macherey–Nagel precoated TLC plates
(
the Cu-catalyzed S-arylation of diaryl disulfides with triar-
ylbismuthanes that we reported previously.15 The first step
of the reaction involves the generation of a bimetallic inter-
I
mediate [(Phen) Cu X ] (A) from copper(I) acetate and
2
2
2
(
(
Sil G25 UV254). Ph Bi (8a), tri(2-tolyl)bismuthane (8g), and PhSeSePh
3
1,10-phenanthroline. Molecular oxygen and the moisture
17
18
12k) were purchased from TCI Fine Chemicals, Japan. 8b–d, 8e,
13
19
17
20
21
21
22
13
21
23
21
present in the air and/or solvent bind efficiently to interme-
8f, 8h, 8i, 8j, 12a, 12b–c, 12d, 12e, 12f, 12g, 12h,
24
25
diate A, which is then oxidized to produce the catalytically
12i, and 12j were prepared according to the reported procedures.
Diaryl selenides 13–21 and 23 are known compounds (unless other-
wise shown below), and their spectroscopic data were identical to
16
active (μ-hydroxide)copper(II) complex B. In cycle A, the
triarylbismuthane undergoes transmetalation with com-
plex B, affording intermediate C; subsequently, oxidative
6g,26,27
those reported in the literature.
2
2
addition of the diselenide (Ar –Se–Se–Ar ) affords the cop-
per(III) intermediate E. Intermediate E undergoes reductive
elimination to give the product, with regeneration of the bi-
metallic intermediate A. An alternative cycle B is also possi-
ble: in this, the ligand-exchange reaction of B with the dia-
ryl diselenide forms the copper(II) complex D; subsequent
oxidative addition of triarylbismuthane gives the cop-
per(III) intermediate E, which presumably undergoes re-
ductive elimination to afford the diaryl selenide.
In conclusion, we have developed a simple copper-cata-
lyzed Se-arylation of diaryl diselenides with triarylbis-
muthane under aerobic conditions in the absence of any
additive. All three aryl groups of the bismuth reagent and
both the selanyl groups on the diaryl diselenide participat-
ed in the reaction. Bismuthanes and diselenides with vari-
ous functional groups afforded the corresponding cross-
coupling products in satisfactory yields. Studies on reac-
tions of triarylbismuthanes with other coupling partners in
the presence of the catalytic system are in progress.
Tris(2-benzo[b]thienyl)bismuthane (8k)
A solution of 1-benzothiophene (4.02 g, 30 mmol) in dry Et O (50 mL)
was cooled to –80 °C, and a 1.6 M solution of BuLi in hexane (20.6 mL,
2
33 mmol) was added dropwise under argon. The mixture was stirred
for 3 h, warmed to –10 °C, and a solution of BiCl (3.15 g, 10 mmol) in
dry THF was added dropwise at –10 °C. The mixture was then stirred
for a further 20 h at r.t. and then diluted with CHCl (70 mL). The reac-
3
3
tion was quenched with H O (1 mL), and anhyd MgSO was added to
2
4
the mixture, which was refluxed for 5 min. The supernatant was re-
moved by decantation. This treatment was repeated three times, and
then the separated supernatant solution was concentrated under re-
duced pressure. The residue was recrystallized (CHCl ) to give color-
less needles; yield: 2.8 g (46%); mp >280 °C (CHCl3).
3
1
H NMR (400 MHz, CDCl ): δ = 7.84 (d, J = 7.3 Hz, 3 H, Ar-H), 7.79 (d,
3
J = 6.8 Hz, 3 H, Ar-H), 7.77 (s, 3 H, Ar-H), 7.33 (td, J = 7.3, 1.5 Hz, 6 H,
Ar-H).
13
C NMR (100 MHz, CDCl ): δ = 146.1 (s), 141.8 (s), 135.1 (d), 124.3
3
(d), 124.2 (d), 123.2 (d), 122.1 (d), 96.1 (s).
+
MS (EI): m/z (%) = 266 (100) [M – C H BiS] , 134 (58).
8
5
Anal. Calcd for C24H15BiS : C, 47.37; H, 2.48. Found: C, 47.41; H, 2.50.
3
Asymmetric Diaryl Selenides 13–26: General Procedure
Melting points were determined on a Yanagimoto micro melting
A solution of the appropriate triarylbismuthane 8 (0.5 mmol), disele-
nide 12 (0.75 mmol), CuOAc (0.05 mmol), and 1,10-phenanthroline
(0.05 mmol) in DMSO (5 mL) was heated at 100 °C under air for the
appropriate time (see Table 2) until the starting material was com-
pletely consumed (TLC). After dilution with CH Cl (50 mL) and H O
1
point hot-stage apparatus (MP-S3) and are uncorrected. H NMR (in-
13
ternal standard TMS; δ = 0.00) and C NMR (internal standard CDCl3;
δ = 77.00) spectra were recorded on JEOL JNM-AL400 (400 MHz and
1
00 MHz) spectrometers in CDCl unless otherwise stated. Mass spec-
3
2
2
2
tra (MS) were obtained on a JEOL JMP-DX300 instrument (70 eV, 300
(30 mL), the mixture was separated and the aqueous layer was ex-
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Synthesis
M. Matsumura et al.
Paper
1
tracted with CH Cl2 (2 × 30 mL). The organic layers were combined,
H NMR (400 MHz, CDCl ): δ = 7.57–7.55 (m, 2 H, Ar-H), 7.46–7.40
2
3
washed with 5% aq NH (30 mL) and H O (30 mL), dried (MgSO ), and
(m, 4 H, Ar-H), 7.37–7.32 (m, 3 H, Ar-H).
3
2
4
concentrated under reduced pressure. The crude residue was purified
by column chromatograph (silica gel) to give diaryl selenides 26 (hex-
ane), 22 (hexane–CH Cl , 10:1), 19, 23 (hexane–CH Cl , 5:1), 13–18,
13
C NMR (100 MHz, CDCl ): δ = 137.8 (s), 134.8 (d), 131.0 (d), 129.7
3
2
3
(d), 128.7 (q, JF = 21 Hz), 128.6 (s), 128.5 (d), 125.9 (q, JF = 4.1 Hz),
2
2
2
2
124.1 (q, J = 272 Hz).
1
F
2
0, 21, 24, and 25 (hexane–CH Cl , 3:1).
2 2
+
MS (EI): m/z (%) = 302 (100) [M ], 281 (14), 222 (100).
+
Phenyl 4-Tolyl Selenide (13)6g
HRMS: m/z [M ] calcd for C13
H
9
F
3
Se: 301.9822; found: 301.9844.
Pale-yellow oil; yield: 323 mg (87%; Table 2, entry 2) or 319 mg (86%;
Phenyl 2-Tolyl Selenide (18)6g
Table 2, entry 12); R = 0.3 (hexane–CH Cl , 5:1).
f
2
2
1
Pale-yellow oil; yield: 325 mg (88%; Table 2, entry 6) or 312 mg (84%,
H NMR (400 MHz, CDCl ): δ = 7.44–7.42 (m, 4 H, Ar-H), 7.25–7.24
3
entry 16); R = 0.3 (hexane–CH Cl , 5:1).
f
2
2
(m, 3 H, Ar-H), 7.11 (d, J = 8.2 Hz, 2 H, Ar-H), 2.34 (s, 3 H, Me).
1H NMR (400 MHz, CDCl
): δ = 7.41–7.38 (m, 2 H, Ar-H), 7.35 (d, J =
13
3
C NMR (100 MHz, CDCl ): δ = 137.6 (s), 133.8 (d), 132.1 (s), 132.0
3
7.2 Hz, 1 H, Ar-H), 7.27–7.21 (m, 4 H, Ar-H), 7.18 (dt, J = 7.2, 1.4 Hz, 1
(d), 130.1 (d), 129.2 (d), 126.8 (d), 126.7 (s), 21.1 (q).
H, Ar-H), 7.05 (dt, J = 7.2, 1.4 Hz, 1 H, Ar-H), 2.39 (s, 3 H, Me).
+
MS (EI): m/z (%) = 248 (80) [M ], 232 (55), 168 (62), 83 (100).
13
C NMR (100 MHz, CDCl ): δ = 139.8 (s), 133.7 (d), 132.7 (d), 131.7
3
+
HRMS: m/z [M ] calcd for C 3H12Se: 248.0104; found: 248.0132.
1
(s), 130.8 (s), 130.2 (d), 129.3 (d), 127.7 (d), 127.1 (d), 126.7 (d), 22.3
q).
(
4
-Methoxyphenyl Phenyl Selenide (14)6g
+
MS (EI): m/z (%) = 248 (100) [M ], 168 (44), 91 (44).
Colorless oil; yield: 316 mg (80%; Table 2, entry 1) or 327 mg (83%,
entry 11); R = 0.3 (hexane–CH Cl , 3:1).
+
HRMS: m/z [M ] calcd for C13H12Se: 248.0104; found: 248.0112.
f
2
2
1
H NMR (400 MHz, CDCl ): δ = 7.50 (d, J = 8.3 Hz, 2 H, Ar-H), 7.32 (d,
Mesityl Phenyl Selenide (19)26
3
J = 6.3 Hz, 2 H, Ar-H), 7.22–7.16 (m, 3 H, Ar-H), 6.85 (d, J = 8.3 Hz, 2 H,
Ar-H), 3.79 (s, 3 H, OMe).
Yellow oil; yield: 339 mg (82%; Table 2, entry 7) or 355 mg (86%, entry
1
7); R = 0.5 (hexane–CH Cl , 5:1).
f
2
2
13
C NMR (100 MHz, CDCl ): δ = 159.7 (s), 136.5 (d), 133.2 (s), 130.9
3
1
H NMR (400 MHz, CDCl ): δ = 7.22–7.04 (m, 5 H, Ar-H), 6.99 (s, 2 H,
3
(d), 129.1 (d), 126.4 (d), 119.9 (s), 115.1 (d), 55.2 (q).
Ar-H), 2.44 (s, 6 H, Me), 2.28 (s, 3 H, Me).
+
MS (EI): m/z (%) = 264 (92) [M ], 221 (10), 184 (100), 169 (52).
13
C NMR (100 MHz, CDCl ): δ = 143.6 (s), 139.0 (s), 133.4 (s), 129.0 (d),
3
+
HRMS: m/z [M ] calcd for C 3H12OSe: 264.0053; found: 264.0061.
1
128.8 (d), 128.4 (d), 126.8 (s), 125.3 (d), 24.1 (q), 21.1 (q).
+
MS (EI): m/z (%) = 276 (100) [M ], 248 (38), 204 (42).
4
-Chlorophenyl Phenyl Selenide (15)6g
+
HRMS: m/z [M ] calcd for C15H16Se: 276.0417; found: 276.0409.
Colorless oil; yield: 342 mg (85%; Table 2, entry 3) or 347 mg (86%,
entry 13); R = 0.3 (hexane–CH Cl , 5:1).
f
2
2
1
-Naphthyl Phenyl Selenide (20)6g
1
H NMR (400 MHz, CDCl ): δ = 7.46–7.44 (m, 2 H, Ar-H), 7.36 (d, J =
3
Colorless oil; yield: 383 mg (90%; Table 2, entry 8) or 361 mg (85%,
entry 18); R = 0.3 (hexane–CH Cl , 5:1).
1H NMR (400 MHz, CDCl
8.2 Hz, 2 H, Ar-H), 7.28–7.26 (m, 3 H, Ar-H), 7.21 (d, J = 8.2 Hz, 2 H, Ar-
f
2
2
H).
13
3
): δ = 8.34–8.33 (m, 1 H, Ar-H), 7.84–7.82
C NMR (100 MHz, CDCl ): δ = 134.1 (d), 134.0 (d), 133.5 (s), 133.2
3
(m, 2 H, Ar-H), 7.75 (d, J = 7.3 Hz, 1 H, Ar-H), 7.51–7.46 (m, 2 H, Ar-H),
(d), 130.6 (s), 129.5 (s), 129.4 (d), 127.6 (d).
7.37–7.32 (m, 3 H, Ar-H), 7.21–7.13 (m, 3 H, Ar-H).
+
MS (EI): m/z (%) = 268 (60) [M ], 188 (80), 152 (46).
13
C NMR (100 MHz, CDCl ): δ = 134.1 (s), 134.1 (s), 133.8 (d), 131.7
3
+
HRMS: m/z [M ] calcd for C H ClSe: 267.9558; found: 267.9574.
12
9
(d), 131.6 (s), 129.4 (s), 129.3 (d), 129.2 (d), 128.5 (d), 127.6 (d), 126.9
(
d), 126.8 (d), 126.3 (d), 126.0 (d).
Ethyl 4-(Phenylselanyl)benzoate (16)6g
+
MS (EI): m/z (%) = 276 (38) [M ], 204 (40), 83 (100).
Colorless oil; yield: 357 mg (78%; Table 2, entry 4) or 372 mg (81%,
+
HRMS: m/z [M ] calcd for C16H12Se: 284.0104; found: 284.0110.
entry 14); R = 0.3 (hexane–CH Cl , 1:1).
f
2
2
IR (neat): 2980, 1717, 1271, 1105 cm–1
.
-(Phenylselanyl)thiophene (21)6g
2
1
H NMR (400 MHz, CDCl ): δ = 7.88 (d, J = 8.2 Hz, 2 H, Ar-H), 7.58–
3
Colorless oil; yield: 294 mg (82%; Table 2, entry 9) or 256 mg (72%,
7.55 (m, 2 H, Ar-H), 7.37–7.25 (m, 5 H, Ar-H), 4.35 (q, J = 7.3 Hz, 2 H,
entry 19); R = 0.6 (hexane–EtOAc, 4:1).
f
OEt), 1.37 (t, J = 7.3 Hz, 3 H, OEt).
1
H NMR (400 MHz, CDCl ): δ = 7.46 (dd, J = 5.4, 0.9 Hz, 1 H, Ar-H),
3
13
C NMR (100 MHz, CDCl ): δ = 166.2 (s), 139.4 (s), 134.8 (d), 130.4
3
7.34–7.30 (m, 3 H, Ar-H), 7.24–7.16 (m, 3 H, Ar-H), 7.04 (dd, J = 5.4,
.9 Hz, 1 H, Ar-H).
(d), 130.1 (d), 129.6 (d), 128.8 (s), 128.6 (s), 128.4 (d), 60.9 (t), 14.3 (q).
3
+
MS (EI): m/z (%) = 306 (95) [M ], 261 (38), 232 (24), 83 (100).
13
C NMR (100 MHz, CDCl ): δ = 137.0 (s), 133.5 (s), 132.0 (d), 129.9
3
+
HRMS: m/z [M ] calcd for C15H14O Se: 306.0159; found: 306.0151.
(d), 129.2 (d), 128.3 (d), 126.7 (d), 123.1 (s).
2
+
MS (EI): m/z (%) = 240 (100) [M ], 160 (90).
Phenyl 4-(Trifluoromethyl)phenyl Selenide (17)6g
+
HRMS: m/z [M ] calcd for C H SSe: 239.9512; found: 239.9519.
10
8
Colorless oil; yield: 403 mg (89%; Table 2, entry 5) or 384 mg (85%,
entry 15); R = 0.4 (hexane).
f
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Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 730–736

7
35
Synthesis
M. Matsumura et al.
Paper
13
2-(Phenylselanyl)benzo[b]thiophene (22)
C NMR (100 MHz, CDCl ): δ = 143.9 (s), 139.1 (s), 136.5 (s), 134.0 (s),
3
1
29.9 (d), 128.9 (d), 126.4 (s), 125.2 (d), 24.1 (q), 21.4 (q), 21.1 (q).
Colorless oil; yield: 368 mg (85%; Table 2, entry 10) or 322 mg (74%,
+
entry 20); R = 0.6 (hexane–CH Cl , 2:1).
MS (EI): m/z (%) = 290 (100) [M ], 288 (50).
f
2
2
1
+
H NMR (400 MHz, CDCl ): δ = 7.77–7.74 (m, 2 H, Ar-H), 7.51 (s, 1 H,
HRMS: m/z [M ] calcd for C16H18Se: 290.0574; found: 290.0582.
3
Ar-H), 7.49–7.46 (m, 2 H, Ar-H), 7.36–7.30 (m, 2 H, Ar-H), 7.28–7.24
Acknowledgment
(m, 3 H, Ar-H).
1
3
C NMR (100 MHz, CDCl ): δ = 143.8 (s), 140.2 (s), 132.2 (d), 131.7 (s),
This work was supported by the Institute of Pharmaceutical Life Sci-
ences, Aichi Gakuin University, and by the Special Research Found of
Hokuriku University.
3
1
1
31.4 (d), 129.3 (d), 127.3 (d), 126.9 (s), 124.7 (d), 124.4 (d), 123.3 (d),
21.8 (d).
+
MS (EI): m/z (%) = 290 (38) [M ], 210 (100).
+
HRMS: m/z [M ] calcd for C14H10SSe: 289.9668; found: 289.9659.
Supporting Information
1
-Methoxy-4-[(4-tolyl)selanyl]benzene (23)27
Colorless prisms (hexane); yield: 355 mg (85%; Table 2, entry 21) or
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0035-1561280.
S
u
p
p
o
nrtIo
i
g
f
rm oaitn
S
u
p
p
ortioIgnfmr oaitn
3
42 mg (82%, entry 22); mp 57–59 °C; R = 0.6 (hexane–CH Cl , 2:1).
f
2
2
1
H NMR (400 MHz, CDCl ): δ = 7.46 (d, J = 8.3 Hz, 2 H, Ar-H), 7.28 (d,
3
References
J = 8.3 Hz, 2 H, Ar-H), 7.04 (d, J = 8.3 Hz, 2 H, Ar-H), 6.83 (d, J = 8.8 Hz,
2
H, Ar-H), 3.80 (s, 3 H, OMe), 2.30 (s, 3 H, Me).
(
1) (a) Wirth, T. Organoselenium Chemistry: Synthesis and Reac-
13
C NMR (100 MHz, CDCl ): δ = 159.5 (s), 136.6 (s), 135.7 (d), 131.8
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Metals in Organic Synthesis; Yamamoto, H.; Oshima, K., Eds.;
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3
(d), 130.0 (d), 128.9 (s), 120.9 (s), 115.0 (d), 55.2 (q), 21.08 (q).
+
MS (EI): m/z (%) = 278 (90) [M ], 276 (50), 198 (100).
+
HRMS: m/z [M ] calcd for C14H14OSe: 278.0210; found: 278.0218.
Ethyl 4-{[4-(Trifluoromethyl)phenyl]selanyl}benzoate (24)
Colorless oil; yield: 510 mg (91%; Table 2, entry 23) or 503 mg (90%,
entry 24); R = 0.4 (hexane–CH Cl , 1:1).
f
2
2
IR (neat): 2983, 1717, 1396, 1325, 1124 cm–1
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(
(
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H NMR (400 MHz, CDCl ): δ = 7.95 (d, J = 8.2 Hz, 2 H, Ar-H), 7.57–
3
7.45 (m, 6 H), 4.38 (q, J = 7.3 Hz, 2 H, Et), 1.39 (t, J = 7.3 Hz, 3 H, Et).
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3
C NMR (100 MHz, CDCl ): δ = 166.0 (s), 136.5 (s), 135.3 (s), 133.0 (d),
101, 2125.
3
2
3
1
32.5 (d), 130.5 (d), 129.9 (s), 129.9 (q, J = 33.1 Hz), 126.2 (q, J = 3.3
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F
F
1
Hz), 123.9 (q, J = 272.3 Hz), 61.1 (t), 14.3 (q).
F
+
MS (EI): m/z (%) = 374 (10) [M ], 372 (50), 329 (55).
4
669. (b) Engman, L.; Cotgreave, I.; Angulo, M.; Taylor, C. W.;
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+
HRMS: m/z [M ] calcd for C16H13F O Se: 374.0033; found: 374.0028.
3
2
(
1-Methoxy-4-{[4-(trifluoromethyl)phenyl]selanyl}benzene (25)
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2
2
2
2
1
5) or 424 mg (85%, entry 26); mp 81–83 °C; R = 0.5 (hexane–CH Cl ,
:1).
f
2
2
H NMR (400 MHz, CDCl ): δ = 7.55 (d, J = 8.8 Hz, 2 H, Ar-H), 7.41 (d,
3
J = 8.3 Hz, 2 H, Ar-H), 7.31 (d, J = 8.3 Hz, 2 H, Ar-H), 6.91 (d, J = 8.8 Hz,
(
2
H, Ar-H), 3.83 (s, 3 H, OMe).
1
3
C NMR (100 MHz, CDCl ): δ = 160.4 (s), 139.5 (s), 137.7 (d), 129.5
3
2011, 111, 1596. (c) Beletskaya, I. P.; Ananikov, V. P. In Catalyzed
2
3
1
(d), 128.1 (q, J = 32.3 Hz), 125.7 (q, J = 4.1 Hz), 124.2 (q, J = 271.5
F
F
F
Carbon–Heteroatom Bond Formation; Yudin, A. K., Ed.; Wiley-
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+
MS (EI): m/z (%) = 332 (95) [M ], 330 (55), 252 (100).
+
HRMS: m/z [M ] calcd for C14H11F3OSe: 331.9927; found: 331.9930.
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Mesityl 2-Tolyl Selenide (26)
(
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3
67 mg (85%, entry 28); mp 59–61 °C; R = 0.5 (hexane).
f
1
H NMR (400 MHz, CDCl ): δ = 7.11 (d, J = 6.8 Hz, 1 H, Ar-H), 7.01 (t, J =
3
6
.8 Hz, 1 H, Ar-H), 7.00 (s, 2 H, Ar-H), 6.88 (t, J = 7.8 Hz, 1 H, Ar-H),
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©
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