Magnesium-Induced Copper-Catalyzed Synthesis of Unsymmetrical Diaryl Chalcogenide Compounds from Aryl Iodide via Cleavage of the Se-Se or S-S Bond

Article abstract of DOI:10.1021/jo030300+

The methodology for a copper-catalyzed preparation of diaryl chalcogenide compounds from aryl iodides and diphenyl dichalcogenide molecules is reported. Unsymmetrical diaryl sulfide or diaryl selenide can be synthesized from aryl iodide and PhYYPh (Y = S, Se) with a copper catalyst (CuI or Cu₂O) and magnesium metal in one pot. This reaction can be carried out under neutral conditions according to an addition of magnesium metal as the reductive reagent. Furthermore, it is efficiently available for two monophenylchalcogenide groups generated from diphenyl dichalcogenide.

Full text of DOI:10.1021/jo030300+

Ma gn esiu m -In d u ced Cop p er -Ca ta lyzed Syn th esis of
Un sym m etr ica l Dia r yl Ch a lcogen id e Com p ou n d s fr om Ar yl Iod id e
via Clea va ge of th e Se-Se or S-S Bon d
Nobukazu Taniguchi* and Tetsuo Onami
Department of Chemistry, Fukushima Medical University, Fukushima 960-1295, J apan
taniguti@fmu.ac.jp
Received September 23, 2003
The methodology for a copper-catalyzed preparation of diaryl chalcogenide compounds from aryl
iodides and diphenyl dichalcogenide molecules is reported. Unsymmetrical diaryl sulfide or diaryl
selenide can be synthesized from aryl iodide and PhYYPh (Y ) S, Se) with a copper catalyst (CuI
or Cu O) and magnesium metal in one pot. This reaction can be carried out under neutral conditions
2
according to an addition of magnesium metal as the reductive reagent. Furthermore, it is efficiently
available for two monophenylchalcogenide groups generated from diphenyl dichalcogenide.
In tr od u ction
the generated compounds are symmetric molecules and
have the characters of both stability and ease of handling.
Regrettably, the use of these derivatives for organochal-
cogenation of aryl halide is confined to a synthetic method
with one chalcogenide-group by stoichiometric metal
reagents.7 Therefore, a catalytic preparation by the
availability of two dichalcogenide molecules has been
little developed up to now (Figure 1). On the contrary,
The construction of an aryl-heteroatom bond is an
important study and a number of reports have been
known.1,2 Similarly, a transition-metal-catalyzed prepar-
ation of aryl chalcogenide has been also developed by
,8
3
various methods so far. These compounds are usually
synthesized from aryl halide and thiol or selenol by a
copper catalyst or other transition metals under basic
conditions. However, a catalytic process under neutral
conditions has been rarely explored. Actually, to promote
the reaction with the present method, it is necessary that
4
5
9
in a catalytic addition to alkyne, or in a phenylselenation
of alkyl halide with diphenyl diselenide,10 the efficient
use of these molecules has been reported.
In the phenylchalcogenation of aryl halide, to exploit
two groups in diphenyl dichalogenide, the requirement
is an application of a metal catalyst with two abilities as
follows. One is a cleavage of the chalcogen-chalcogen
bond, and the other is an oxidative addition to aryl halide.
To satisfy these qualifications, it seems that the employ-
ment of a transition-metal catalyst having a capability
a compound with an organochalcogen-metal bond should
be employed.6
On the other hand, RYH (Y ) S, Se) has a property of
easy conversion to RYYR by atmosphere oxygen. Herein,
*
Corresponding author.
(1) For a review on an aryl-chalcogen bond formation, see: Com-
prehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon
1
1
Press, Ltd.: New York, 1991; Vol. 6.
to insert into the dichalcogen bond is the most suitable.
(
2) For selected examples of an aryl-heteroatom bond formation,
see: (a) Yang, B. H.; Buchwald, S. L. J . Organomet. Chem. 1999, 576,
25-146. (b) Marcoux, J .-F.; Doye, S.; Buchwald, S. L. J . Am. Chem.
Soc. 1997, 119, 10539-10539. (c) Hartwig, F.; Mann, G. J . Org. Chem.
997, 62, 5413-5418. (d) Palucki, M.; Wolfe, J . P.; Buchwald, S. L. J .
Am. Chem. Soc. 1997, 119, 3395-3396.
3) (a) Krief, A. In Comprehensive Organometallic Chemistry II; Abel,
However, it is possible that production of complexes by
the transition metal inserts into dichalcogenide prevents
promoting the next step owing to the firmness of the
1
1
(
(6) (a) Nishiyama, Y.; Tokunaga, K.; Sonoda, N. Org. Lett. 1999, 1,
1725-1727. (b) Kosugi, M.; Ogata, T.; Terada, M.; Sano, H.; Migita,
T. Bull. Chem. Soc. J pn. 1985, 58, 3657-3658. (c) Beletskaya, I. P.;
Sigeev, A. S.; Peregudov, A. S.; Petrovskii, P. V. Tetrahedron Lett. 2003,
44, 7039-7041.
(7) For an example of phenylthiolation of ArI, see: Okamoto, Y.;
Yano, T. J . Organomet. Chem. 1971, 29, 99-103.
(8) For examples of phenylselenation or thiolation of alkyl halide,
see: (a) Bao, W.; Zheng, Y.; Zhang, Y.; Zhou, J . Tetrahedron Lett. 1996,
37, 9333-9334. (b) Bao, W.; Zhang, Y. Synlett 1996, 1187-1189. (c)
Chawdhury, S.; Roy, S. Tetrahedron Lett. 1997, 38, 2149-2152.
(9) (a) Kuniyasu, H.; Ogawa, A.; Miyazaki, S.-i.; Ryu, I.; Kanbe, N.;
Sonoda, N. J . Am. Chem. Soc. 1991, 113, 9796-9803. (b) Ogawa, A.;
Kuniyasu, H.; Sato, K.; Sonoda, N.; Hirao, T. J . Org. Chem. 1997, 62,
8361-8365. (c) Arisawa, M.; Yamaguchi, M. Org. Lett. 2001, 3, 763-
764. (d) Ananikov, V. P.; Beletskaya, I. P.; Aleksandrov, G. G.;
Eremenko, I. L.; Organometallics 2003, 22, 1414-1421.
(10) (a) Kundu, A.; Roy, S. Organometallics 2000, 19, 105-107. (b)
Y. Nishino, T.; Okada, M.; Kuroki, T.; Watanabe, T.; Nishiyama, Y.;
Sonoda, N. J . Org. Chem. 2002, 67, 8696-8698. (c) Ranu, B. C.;
Mandal, T.; Samanta, S. Org. Lett. 2003, 5, 1439-1441.
E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press, Ltd.: New
York, 1995; Vol. 11, Chapter 13. (b) Wirth, T., Ed. Organoselenium
Chemistry; Topics in Current Chemistry 208; Springer-Verlag: Heidel-
berg, 2000. (c) Paulmier, C. In Selenium Reagents and Intermediates
in Organic Synthesis; Baldwin, J . E., Ed.; Organic Chemistry Series
4
; Pergamon Press Ltd.: Oxford, 1986.
4) (a) Suzuki, H.; Abe, H.; Osuka, A. Chem. Lett. 1981, 151-152.
b) Gujadhur, R. K.; Venkataruman, D. Tetrahedron Lett. 2003, 44,
(
(
8
1-84. (c) Bowman, W. R.; Heaney, H.; Smith, P. H. G. Tetrahedron
Lett. 1984, 25, 5821-5824. (d) Suzuki, H.; Abe, H.; Osuka, A. Chem.
Lett. 1980, 1363-1364. (e) Kwong, F. Y.; Buchwald, S. L. Org. Lett.
2
002, 4, 3517-3520.
(
5) (a) Kosugi, M.; Shimizu, T.; Migita, T.; Chem. Lett. 1978, 13-
1
4. (b) Migita, T.; Shimizu, T.; Asami, Y.; Shiobara, J .-i.; Kato, Y.;
Kosugi, M. Bull Chem. Soc. J pn. 1980, 53, 1385-1389. (c) Cristau, H.
J .; Chabaud, B.; Christol, C. H. Synthesis 1981, 892-894. (d) Zheng,
N.; McWillians, J . C.; Fleitz, F. J .; Armstrong, J . D., III; Volante, R.
P. J . Org. Chem. 1998, 63, 9606-9607. (e) Bowman, W.; Heaney, H.;
Smith, P. H. G. Tetrahedron Lett. 1984, 25, 5821-5824. (f) Ciatini, P.
G.; Morera, E.; Ortar, G. Tetrahedron Lett. 1995, 36, 4133-4136.
1
0.1021/jo030300+ CCC: $27.50 © 2004 American Chemical Society
Published on Web 01/10/2004
J . Org. Chem. 2004, 69, 915-920
915

Taniguchi and Onami
absence of the copper catalyst and 1a was recovered 98%
yield (entry 2).13
In addition, the employment of other metals (Zn, Al,
Sm, and Sn) instead of magnesium was investigated.
Whereas zinc, aluminum, or samarium gave yields of
5
(
8
4%, 75%, and 80%, respectively, for the formation of 2a
entries 5, 6, and 7), the use of tin was ineffective (entry
). Thus, it was obvious that in the phenylselenation of
aryl iodide with diphenyl diselenide, a combination of
F IGURE 1. Metal-catalyzed phenylchalcogenation of ArI via
insertion to dichalcogen bond.
TABLE 1. Rea ction betw een 2-Iod otolu en e (1a ) a n d
Dip h en yl Diselen id e (2) w ith Cop p er Ca ta lysta
both the copper catalyst (CuI or Cu
gave an excellent result.
2
O) and magnesium
Ap p lica tion to th e Cop p er -Ca ta lyzed P r ep a r a tion
of Dia r yl Selen id es a n d Dia r yl Su lfid es. We next
directed our attention to the preparation of diaryl se-
lenides using this method. The results of the synthesis
entry
1
[Cu]
additive
time (h)
3a c (%)
1a c (%)
2
of diaryl selenides with the Cu O catalyst and magne-
CuI
none
CuI
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
none
Mg
Mg
Mg
Zn
Al
Sm
Sn
12
12
30
30
30
30
30
30
0
0
97
98
8
sium are presented in Table 2. Various unsymmetrical
diaryl selenides 3 were obtained in 53-95% yields by
substituted aryl iodides 1 and diphenyl diselenide (2)
b
2
3
4
5
6
7
8
87
92
54
75
80
trace
4
35
16
5
2
treated with Cu O (5 mol %), bpy (10 mol %), and
magnesium in DMF at 110 °C for 18-36 h (entries 1-16).
Similarly, the above method can be applied to the
synthesis of unsymmetrical diaryl sulfides 5 with diaryl
disulfide (4a and 4b). In this reaction, the CuI catalyst
94
a
The mixture of 1a (0.3 mmol), 2 (0.15 mmol), and copper
catalyst in DMF (0.5 mL) was stirred at 110 °C, and Cu2O (5 mol
2
has been employed because the Cu O catalyst lowered
%), CuI (10 mol %), and additive metals (0.6 mmol) were used.
the yield of diaryl sulfide 5.14 The CuI-catalyzed reaction
between aryl iodide 1 and diaryl disulfide 4 afforded the
corresponding sulfides in good yields (Table 3). Also, this
condition was accessible to synthesize n-butyl aryl sul-
fides from aryl iodides and di-n-butyl disulfide (4c)
b
c
bpy was not added. Isolated yields after silica gel chromatog-
raphy.
metal-chalcogen bond. As a solution to this problem, we
have found that the addition of magnesium metal could
carry out a copper-catalyzed phenylselenation of aryl
iodide with diphenyl diselenide under neutral condi-
tions.12
In this paper, we wish to report a convenient synthesis
of unsymmetrical diaryl chalcogenides with 0.5 equiv of
diphenyl diselenide or disulfide by a copper catalyst and
magnesium and a study of the detailed reaction mecha-
nism.
(entries 4 and 14). Moreover, in the reaction of 1-bromo-
4
-iodobenzene, two halogen groups could be converted to
a phenylthio-substituent in 75% yield by the use of 1.0
equiv of 4a (entry 11).15 Unfortunately, in the case of
4
-nitro-1-iodobenzene, a significant decrease in the ob-
tained yield was observed, and the starting material 1
was recovered in 70% yield (entry 15). However, on the
whole, unsymmetrical diaryl sulfides or diaryl selenides
could be synthesized from aryl iodide and 0.5 equiv of
2
(PhY) by the combination of the copper catalyst and
Resu lts a n d Discu ssion
magnesium.
P r op osed Rea ction Mech a n ism of th e Cop p er -
Ca ta lyzed P h en ylselen a tion of Ar yl Iod id e. To in-
vestigate the present reaction mechanism, we examined
the phenylselenation of aryl iodide, and subsequent
experiments were carried out in detail. As shown in Table
2
Syn th esis of Diar yl Selen ide fr om Ar I an d (P h Se) .
To obtain a diaryl selenide from aryl iodide and diphenyl
diselenide, we searched for a reaction condition with a
copper catalyst. First, when 2-iodotoluene (1a ) and
diphenyl diselenide (2) were treated with CuI (10 mol
) in DMF at 110 °C for 12 h, the expected product was
not obtained at all and 1a was recovered in 97% yield
entry 1 in Table 1). Fortunately, the addition of mag-
nesium (0.6 mmol) to the reaction mixture, in the reaction
between 1a (0.3 mmol) and 2 (0.15 mmol), could afford
the corresponding phenyl 2-tolyl selenide (3a ) in 87%
4
, some interesting results were obtained.
%
In the phenylselenation of 2-iodotoluene (1a ), when
Cu O was employed, the reaction was not promoted, and
2
(
both 1a and diphenyl diselenide (2) were recovered
unconsumed (entries 1 and 2).
Furthermore, the case with Cu(powder) was re-
searched. Stoichiometric Cu (100 mol %) gave 3a in 80%
yield (entry 3), and the use of Cu (50 mol %) also yielded
yield after 30 h (entry 3). The use of Cu
gave 3a in 92% yield (entry 4). However, other copper
2
salts (CuOTf, CuBr, CuCl, CuBr , CuCl , and Cu(OAc) )
2
O (5 mol %) also
2
2
(
13) (a) Olah, G. A.; Ohannesian, L.; Arvanaghi, M. Chem. Rev. 1987,
were not effective for this reaction. Remarkably, mag-
nesium alone could not promote this reaction in the
8
7, 671-686. (b) Wakefield, B. J . Ed. Organomagnesium Methods in
Organic Synthesis; Academic Press: San Diego, 1995. (c) Soboureau,
C.; Troupel, M.; Sibille, S.; d’Incan, E.; P e´ richon, J . J . Chem. Soc.,
Chem. Commun. 1989, 895-896.
(11) (a) Kumar, R.; Mabrouk, H. E.; Tuck, D. G.; J . Chem. Soc.,
(14) In the reaction between 2-iodotoluene (1a ) and diphenyl dis-
Dalton Trans. 1988, 1045-1047. (b) Zanella, R.; Ros, R.; Graziani, M.
Inorg. Chem. 1973, 12, 2736-2738. (c) Mashima, K.; Nakayama, Y.;
Kanehisa, N.; Kai, Y.; Nakamura, A. J . Chem. Soc., Chem. Commun.
ulfide (2) with Cu
the yield of phenyl 2-tolyl sulfide was 25% yield.
(15) The reaction between bromobenzene (0.3 mmol) and (PhS)
mmol) with CuI (10 mol %) and Mg (0.6 mmol) at 110 °C for 48 h
afforded diphenyl sulfide in 34% yield.
2
O (5 mol %) and Mg (0.6 mmol) at 110 °C for 48 h,
2
(0.15
1
993, 1847-1848.
(
12) Taniguchi, N.; Onami, T. Synlett 2003, 829-832.
9
16 J . Org. Chem., Vol. 69, No. 3, 2004

Synthesis of Unsymmetrical Diaryl Chalcogenide Compounds
TABLE 2. P r ep a r a tion of Ar SeP h fr om 1 a n d 2 w ith Cu 2O Ca ta lyst
a
Isolated yields after silica gel chromatography. b Cu2O (10 mol %) was used .
it in 44% (entry 4).16 Thus, it appears that when more
than 50 mol % Cu(0) is used, the redox of Cu(0) and Cu(II)
occurs. Although a catalytic amount Cu (10-30 mol %)
was not effective for this reaction, 2 was consumed by
the catalytic amount (entries 5, 6, and 7). These facts
show that in the use of 10 mol % of Cu(0), the redox of
Cu(0) and Cu(II) is little promoted. On the other hand,
the addition of magnesium in the presence of Cu (10 mol
sium works as the reductive reagent. In the catalytic
cycle, the first step is the generation of Cu(0) from Cu O
2
by the reduction of magnesium, Cu(II)(SePh) is produced
2
by the insertion of Cu(0) into the diselenide bond, and
2
subsequently the reduction of Cu(SePh) by magnesium
converts into Cu(I)SePh.
Similarly, in the use of the CuI catalyst, the role of
magnesium suggests the reduction of a copper complex.
However, as compared with the case of the Cu O catalyst,
2
%) could afford 3a in 87% yield (entry 8). In the case of
a stoichiometric amount of CuI (100 mol %), 2 was used
two pathways are considered in order to form CuSePh,
because CuI itself has the capability to insert into the
Se-Se bond (Figure 2). One process is that Cu(0) is
produced from CuI by the reduction of magnesium as well
up completely, 3a was not obtained, and 1a was recov-
ered in 98% yield (entry 9).17 The catalytic amount did
not provide 3a (entry 10). When magnesium was added
in the absence of the copper catalyst, 1a and 2 were
recovered in yields of 98% and 98% without formation of
any other products (entry 11). Moreover, when 1a and
magnesium in DMF were treated at 110 °C for 24 h, no
Grignard reaction was observed, and ArI and magnesium
metal were recovered (Scheme 1).13 It was proved that
magnesium itself had no ability to cleave the Se-Se bond
and to produce ArMgI in DMF.
2
as the Cu O catalyst. The other is that Cu(I)SePh is
produced after a generated complex Cu(III)I(SePh) via
2
the oxidative addition of CuI to (PhSe) ,is reduced by
2
17
magnesium. In practice, although the CuI catalyst alone
could not carry out the reaction, the addition of magne-
sium after the mixture of 1a , CuI (10 mol %), and 2 was
stirred at 110 °C for 24 h afforded 3a in 80% yield after
From these experimental results, in the phenylselena-
tion with the Cu O catalyst, it can be seen that magne-
2
4
8 h (Scheme 2). In addition, in the course of these steps,
it is also considered that (PhSe) Cu(II) was produced by
2
the redox of Cu(I) and Cu(III). Therefore, it is presumed
that the CuI catalyst can pass through these processes
to produce Cu(I)SePh.
(
(
16) Yamamoto, Y.; Sekine, Y. Can. J . Chem. 1984, 62, 1544-1547.
17) A green participate was produced by the reaction between CuI
2
and (PhSe) .
J . Org. Chem, Vol. 69, No. 3, 2004 917

Taniguchi and Onami
TABLE 3. P r ep a r a tion of Ar yl Su lfid e fr om 1 a n d 4 by Cu I Ca ta lyst
a
Isolated yields after silica gel chromatography. b CuI (15 mol %) was used. c (PhS)2 (1.0 equiv) was used. d Yield of 1,4-
bis(phenylthio)benzene.
TABLE 4. P h en ylselen a tion of 1a w ith Cop p er Ca ta lyst
a
in th e Absen ce of Ma gn esiu m
F IGURE 2. Plausible process to produce CuSePh from CuI.
[Cu]
ArSePh 3a b
ArI 1a b
recovery of 2b
entry
(mol %)
(%)
(%)
(%)
SCHEME 1
1
2
3
4
5
6
7
8
9
Cu2O (100)
(10)
Cu (100)
(50)
(30)
(20)
0
0
80
44
3
1
0
87
0
0
98
97
10
53
94
96
98
7
97
97
2
11
40
81
88
0
c
c
c
c
c
(10)
c,d
(10) + Mg
CuI (100)
(10)
98
97
98
1
89
98
1
1
0
1
c,d
None + Mg
0
a
iodide and Cu(I)SPh.19 Accordingly, Cu(I)SePh works as
an activating species in the catalytic phenylselenation
of aryl iodide.
1
a and 2 were used (0.3 and 0.15 mmol, respectively).
b
c
Isolated yields after silica gel chromatography. Cu (75 µm
powder) was used. Mg (0.6 mmol) was added.
d
Our proposed mechanism for this reaction is outlined
The above-described Cu(I)SePh (100 mol %) can pro-
vide ArSePh 3 in good yields without the addition of
magnesium in the presence of bpy (Table 5).18 The same
result is also observed from the reaction between aryl
in Figure 3. When Cu
the reaction process was considered as follows. After the
Cu O was reduced to Cu(0), the insertion of Cu(0) to
(PhSe) produced Cu(II)(SePh) 8. On account of the fact
2
O was employed as the catalyst,
2
2
2
9
18 J . Org. Chem., Vol. 69, No. 3, 2004

Synthesis of Unsymmetrical Diaryl Chalcogenide Compounds
SCHEME 2
the copper catalyst was reduced by magnesium at each
step, and these processes were the important steps for
the preparation of the aryl-chalcogen bond via cleavage
of the dichalcogenide bond. Thus, in the copper-catalyzed
phenylchalcogenation, the addition of magnesium en-
abled the efficient use of two PhY (Y ) S or Se) groups
generated from diphenyl dichalcogenide under neutral
conditions.
TABLE 5. Rea ction betw een Ar I 1 a n d P h YCu (I)
a
(
Y ) Se or S)
Exp er im en ta l Section
Gen er a l P r oced u r e. All reactions were carried out under
a nitrogen atmosphere. NMR spectra were recorded on a J EOL
EX-270 spectrometer (270 MHz for 1H, 67.5 MHz for C).
Chemical shifts are reported in δ ppm referenced to an internal
13
entry
R
PhYCu
ArYPhb (%)
1
tetramethylsilane standard for H NMR and chloroform-d (δ
1c
2
3
H
H
Me
Me
Se
Se
Se
S
trace
81
82
7
7.0) for 13C NMR. IR spectra were measured by Perkin-Elmer
Spectrum One FT-IR spectrometer.
Cop p er -Ca ta lyzed Syn th esis of Dia r yl Selen id e fr om
4
80
1
Ar yl Iod id e a n d Diselen id e (Ta ble 2). En tr y 4: H NMR
a
The mixture of 1 (0.3 mmol), bpy (0.3 mmol), and PhYCu (0.3
mmol) in DMF (1.0 mL) was stirred at 110 °C. Isolated yields
after silica gel chromatography. bpy was not added.
(
5
CDCl
3
) δ 2.01 (s, 3H), 7.07 (t, J ) 7.2 Hz, 1H), 7.18-7.25 (m,
b
H), 7.41 (t, J ) 7.2 Hz, 1H), 7.69 (d, J ) 7.2 Hz, 1H), 8.12
c
13
(
1
1
br, 1H), 8.38 (d, J ) 7.2 Hz, 1H); C NMR (CDCl
3
) δ 24.5,
20.9, 124.6, 127.1, 129.3, 129.5, 129.9, 130.0, 130.7, 131.1,
-1
37.4, 168.2; IR (neat) 3289, 3059, 1668, 1581, 1515, 1428 cm
13NOSe: C, 57.94; H, 4.51; N, 4.83.
Found: C, 57.85; H, 4.53; N, 4.80.
.
Anal. Calcd for C14
H
1
En tr y 5: H NMR (CDCl
3
) δ 3.39 (s, 3H), 4.56 (s, 2H), 7.14
(
1
1
t, J ) 8.4 Hz, 1H), 7.24-7.29 (m, 4H), 7.34 (d, J ) 8.4 Hz,
H), 7.41-7.45 (m, 3H); 13C NMR (CDCl
) δ 58.1, 74.4, 127.3,
27.4, 128.4, 128.6, 129.3, 130.9, 131.7, 133.1, 133.8, 139.3;
3
-
1
IR (neat) 3057, 1577, 1476 cm . Anal. Calcd for C14H14OSe:
C, 60.66; H, 5.09. Found: C, 60.77; H, 5.12.
1
En tr y 7: H NMR (CDCl
3
) δ 7.22-7.38 (m, 6H), 7.57-7.66
) δ 126.3, 126.6, 126.7, 127.7, 128.6,
29.1, 129.6, 131.5, 132.0, 133.3, 135.5; IR (neat) 1570, 1476,
(
1
1
m, 3H); 13C NMR (CDCl
3
-
1
313 cm . Anal. Calcd for C13
9 3
H F Se: C, 51.84; H, 3.01.
Found: C, 51.54; H, 3.16.
1
En tr y 11: H NMR (CDCl
3
) δ 7.24-7.37 (m, 3H), 7.40-7.47
) δ 125.8, 125.8,
25.9, 126.0, 128.5, 128.7, 129.7, 131.0, 134.8; IR (neat) 1601,
(
1
1
m, 4H), 7.55-7.58 (m, 2H); 13C NMR (CDCl
3
-
1
325 cm . Anal. Calcd for C13
H
9
F
3
Se: C, 51.84; H, 3.01.
F IGURE 3. Plausible reaction mechanism.
Found: C, 51.69; H, 3.14.
En tr y 15: H NMR (CDCl
1
3
) δ 7.16-7.20 (m, 1H), 7.26-7.32
that complex 8 is impossible to perform this reaction, it
is reduced by magnesium to readily produce Cu(I)SePh
(m, 3H), 7.47-7.51 (m, 2H), 7.72 (d, J ) 7.9 Hz, 1H), 8.47-
8.49 (m, 1H), 8.66 (br, 1H); 13C NMR (CDCl
) δ 124.2, 127.9,
28.8, 129.5, 129.6, 133.4, 140.0, 148.2, 152.7; IR (neat) 1576,
3
1
1
5
1
1
0 which is the activating species. Finally, the complex
0 is converted into ArSePh by the reaction of ArI, and
-
1
476, 1463, 1438, 1403 cm . Anal. Calcd for C11
6.42; H, 3.87; N, 5.98. Found: C, 56.43; H, 3.97; N, 6.00.
9
H NSe: C,
in this step, the generated CuI provides 10 again through
two ways.
Cop p er -Ca ta lyzed Syn th esis of Dia r yl Su lfid e fr om
Ar yl Iod id e a n d Disu lfid e (Ta ble 3). En tr y 3: H NMR
1
On the other hand, MgY(SePh) 9 is formed by the
reductive reaction of a copper-phenylselenide complex
13
(
CDCl
NMR (CDCl
131.0, 131.3, 135.1, 136.8, 138.7; IR (neat) 1491, 1467 cm .
3
) δ 2.32 (s, 3H), 2.37 (s, 3H), 7.08-7.23 (m, 8H);
C
3
) δ 20.4, 21.0, 126.5, 127.0, 128.5, 129.9, 130.0,
-
1
(8 or 12) by magnesium, and it is reused as the phenylse-
lenium source in the presence of Cu(I)I in the catalytic
Anal. Calcd for C14
H
14S: C, 78.45; H, 6.58. Found: C, 78.40;
system.4a Similarly, it is anticipated that the same
H, 6.61.
En tr y 6: H NMR (CDCl
1
3
) δ 2.05 (s, 3H), 2.29 (s, 3H), 7.00-
mechanism is applicable to the copper-catalyzed synthe-
sis of diaryl sulfide with disulfide compounds. Thus, the
present method is feasible to synthesize ArYPh (Y ) S
or Se) from ArI in good yields by only using 0.5 equiv of
7
1
.11 (m, 5H), 7.43 (t, J ) 8.2 Hz, 1H), 7.57 (d, J ) 7.5 Hz,
H), 8.18 (br, 1H), 8.43 (d, J ) 8.2 Hz, 1H); 13C NMR (CDCl
)
3
δ 20.9, 24.7, 120.8, 120.9, 124.3, 127.8, 127.9, 130.0, 130.5,
-1
1
35.9, 136.5, 139.5, 168.2; IR (neat) 3360, 1693, 1511 cm
Anal. Calcd for C15 15NOS: C, 70.01; H, 5.87; N, 5.44.
Found: C, 69.94; H, 5.98; N, 5.47.
En tr y 7: 1H NMR (CDCl
) δ 7.19 (d, J ) 7.9 Hz, 1H), 7.20-
.43 (m, 7H), 7.68 (d, J ) 7.6 Hz, 1H); C NMR (CDCl
26.2, 126.5, 126.6, 126.7, 128.1, 129.5, 132.0, 132.3, 133.0,
.
(PhY)
2
.
H
In conclusion, we have developed a magnesium-
induced copper-catalyzed synthesis of the unsymmetrical
diaryl selenide or diaryl sulfide from aryl iodide and
diphenyl diselenide or diphenyl disulfide. In this method,
3
1
3
7
1
1
3
) δ
-
1
33.8, 136.7; IR (neat) 1594, 1473, 1440, 1312 cm . Anal.
Calcd for C13
.90.
H
9
F
3
S: C, 61.41; H, 3.57. Found: C, 61.71; H,
(
18) Back, T. G.; Collins, S.; Krishna, M. V.; Law, K.-W. J . Org.
Chem. 1987, 52, 4258-4264.
19) Organic Syntheses; J ohn Wiley & Sons: New York, 1973;
Collect. Vol. 5, pp 107-110.
3
1
(
En tr y 9: mp 46-47 °C; H NMR (CDCl
3.79 (s, 3H), 6.85 (d, J ) 6.5 Hz, 2H), 7.06 (d, J ) 8.2 Hz, 2H),
3
) δ 2.29 (s, 3H),
J . Org. Chem, Vol. 69, No. 3, 2004 919

Taniguchi and Onami
(d, J ) 8.2 Hz, 2H), 7.49 (d, J ) 8.2 Hz, 2H); 13C NMR (CDCl
)
3
7
.12 (d, J ) 8.2 Hz, 2H), 7.35 (d, J ) 6.5 Hz, 2H); 13C NMR
(CDCl
3
) δ 20.9, 55.3, 114.8, 125.6, 129.3, 129.7, 134.3, 136.1,
δ 13.5, 21.9, 30.8, 32.1, 125.4, 125.5, 125.6, 127.1, 142.8; IR
-
1
-1
1
38.0, 159.4; IR (CHCl
3
) 1591, 1492 cm . Anal. Calcd for
(neat) 2961, 1607 cm . Anal. Calcd for C11
H, 5.59. Found: C, 56.66; H, 5.68.
H
13
F
3
S: C, 56.39;
14
C H14OS: C, 73.01; H, 6.13. Found: C, 72.92; H, 6.22.
1
En tr y 13: mp 95-96 °C; H NMR (CDCl
3
) δ 2.38 (s, 3H),
.18-7.22 (m, 4H), 7.37-7.46 (m, 4H); 1 C NMR (CDCl
) δ
1.2, 125.6, 125.7, 125.8, 127.4, 128.5, 129.7, 130.5, 134.2,
3
7
2
1
3
1
Su p p or tin g In for m a tion Ava ila ble: Analytical data ( H
13
and C NMR spectra) and literature citations for known
-
1
39.2; IR (CHCl
3
) 1606, 1326, 1215 cm . Anal. Calcd for
compounds. This material is available free of charge via the
Internet at http://pubs.acs.org.
14 9 3
C H F
S C, 62.67; H, 4.13. Found: C, 62.65; H, 4.15.
1
En tr y 14: H NMR (CDCl
3
) δ 0.94 (t, J ) 7.2 Hz, 3H), 1.43-
1
.54 (m, 2H), 1.61-1.70 (m, 2H), 2.97 (t, J ) 7.4 Hz, 2H), 7.34
J O030300+
9
20 J . Org. Chem., Vol. 69, No. 3, 2004