Indium-mediated cleavage of diphenyl diselenide and diphenyl disulfide: efficient one-pot synthesis of unsymmetrical diorganyl selenides, sulfides, and selenoesters

Article abstract of DOI:10.1016/j.tet.2009.01.072

A convenient and efficient method was developed for the synthesis of alkyl phenyl selenides, sulfides, and selenoesters in one-pot reaction by using indium metal. The reaction showed the selectivity for tert-alkyl, benzylic, and allylic halides over primary and secondary alkyl halides. For the reaction of primary and secondary alkyl iodides and bromides, the yields of selenides were improved by the addition of a catalytic amount of iodine.

Full text of DOI:10.1016/j.tet.2009.01.072

Tetrahedron 65 (2009) 2467–2471
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Tetrahedron
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Indium-mediated cleavage of diphenyl diselenide and diphenyl disulfide:
efficient one-pot synthesis of unsymmetrical diorganyl selenides,
sulfides, and selenoesters
,
Wanida Munbunjong b, Eun Hwa Lee a, Poonlarp Ngernmaneerat b c, Sung Jun Kim a,
,
c
,
a,
*
Gurpinder Singh a, Warinthorn Chavasiri b , Doo Ok Jang
*
a Department of Chemistry, Yonsei University, Wonju 220-710, Republic of Korea
b Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
c Center of Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Bangkok 10330, Thailand
a r t i c l e i n f o
a b s t r a c t
Article history:
A convenient and efficient method was developed for the synthesis of alkyl phenyl selenides, sulfides,
and selenoesters in one-pot reaction by using indium metal. The reaction showed the selectivity for
tert-alkyl, benzylic, and allylic halides over primary and secondary alkyl halides. For the reaction of
primary and secondary alkyl iodides and bromides, the yields of selenides were improved by the addition
of a catalytic amount of iodine.
Received 5 December 2008
Received in revised form 15 January 2009
Accepted 15 January 2009
Available online 21 January 2009
Ó 2009 Elsevier Ltd. All rights reserved.
Keywords:
Alkyl phenyl selenide
Alkyl phenyl sulfide
Alkyl halide
Diphenyl diselenide
Diphenyl disulfide
Indium
1. Introduction
rearrangements, and a variety of useful reactions.5 They have
drawn an increasing attention for their unique properties such as
Interest in organochalcogenides has increased continuously for
their important role in organic synthesis and their useful biological
activities. Organoselenium compounds, for instance, have been
proved to play a role as important therapeutic compounds such as
antiviral and anticancer agents.1 Organochalcogenides have also
emerged as crucial intermediates in the transformations of a variety
of functional groups.2
Much effort has been devoted to accomplish the synthesis of
organochalcogenides, and a number of reports on the preparation
of organochalcogenides have been published.3,4 However, many
preparative methods proceeded with multi-step procedures under
strongly basic or acidic reaction conditions and sometimes suffered
from improper handling of unstable reagents in air and moisture.
Therefore, development of new synthetic methods is required in
organic synthesis for the preparation of organochalcogenides using
stable reagents and one-step procedure under neutral conditions.
Over the past decade, indium metal and its salts have been
chosen as the reagents for carbon–carbon bond formation,
low toxicity and high stability in water and air compared with other
metals. As part of our effort toward developing applications of
indium metal in organic synthesis,6 we developed an indium-me-
diated reaction for preparing unsymmetrical organochalcogenides
from alkyl halides and diphenyl diselenide (diphenyl disulfide).7
Herein, we wish to report an account on a mild and efficient one-
pot procedure for the synthesis of alkyl phenyl selenides, sulfides,
and selenoesters using indium metal under neutral conditions
(Scheme 1).
In
R
ZPh
R
X
+
PhZZPh
CH2Cl2, reflux
X = I, Br, or Cl
Z = Se or S
Scheme 1.
2. Results and discussion
t
We first performed the reaction of BuCl with PhSeSePh under
various reaction conditions as shown in Table 1. The reaction of
* Corresponding authors.
E-mail address: dojang@yonsei.ac.kr (D.O. Jang).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.01.072

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W. Munbunjong et al. / Tetrahedron 65 (2009) 2467–2471
Table 1
diselenide in order to evaluate the scope and limitations of the
t
Reaction of BuCl with PhSeSePh in the presence of indium
present procedure. The results are presented in Table 3. Tertiary
alkyl halides underwent a clean reaction to provide the corre-
sponding alkyl phenyl selenides in high yields (entries 1–5). Note
that the reaction of tert-alkyl halides with metal phenyl seleno-
lates, which were made from the reaction of PhSeSePh with La4m
or Zn,4o or from the reaction of PhSeH with CsOH,4h could not be
achieved even under harsh reaction conditions. It is interesting to
note that the reaction with bridged halides, 1-haloadamantanes,
also proceeded without difficulty (entries 3–5). Various primary
and secondary alkyl halides were examined. In contrast to tertiary
alkyl halides, they were found to be inactive to the present
indium-promoted selenation of alkyl halides (entries 6–9). Benzyl
phenyl selenides were also formed from benzyl bromide and
chloride (entries 10–15). With substituent groups on benzene
In
CH2Cl2
t
t
+
Bu SePh
Bu Cl
PhSeSePh
1
Entry
tBuCl (equiv)
In (equiv)
Temp
Time (h)
Yielda (%)
1
2
3
4
5
6
2.0
2.0
2.0
2.0
2.0
2.0
1.0
1.0
0
0.5
0.1
1.0
Reflux
rt
Reflux
Reflux
Reflux
Reflux
1
3
1
1
1
1
95
99
0
91
20
3b
a
The reaction was analyzed by GC, and the yield was calculated on the base of the
t
amount of BuCl.
b
InCl3 was used instead of In.
t
diphenyl diselenide with 2.0 equiv of BuCl in the presence of an
Table 3
equimolar amount of indium in CH2Cl2 at reflux for 1 h afforded
tert-butyl phenyl selenide (1) in 95% yield, which was determined
on the base of the amount of tBuCl (entry 1). When the reaction was
carried out at ambient temperature, a quantitative yield of the
product was obtained (entry 2), although longer reaction time was
required for completion. In the absence of indium metal, however,
the reaction did not proceed at all, implying that indium acts as
a promoter of the reaction (entry 3). The essential amount of
indium required for efficient promoting of the reaction could be
reduced to 0.5 equiv affording the product in 91% yield (entry 4).
With 0.1 equiv of indium (entry 5) or 1.0 equiv of InCl3, the reaction
was not efficient (entry 6).
Synthesis of alkyl phenyl selenides from alkyl halides
In (1 equiv)
R
SePh
+
PhSeSePh
(1 equiv)
R
X
CH2Cl2, reflux, 1h
(2 equiv)
Entry
RX
RSePh
Yielda (%)
1
2
3
4
5
6
7
8
tBuI
tBuBr
1-Iodoadamantane
1-Bromoadamantane
1-Chloroadamantane
iPrI
1b
1b
2c
2c
2c
3d
4d
5e
99
95 (86)
86 (76)
84 (74)
99 (88)
NR
Cyclohexyl bromide
CH3(CH2)5I
NR
NR
Next, we investigated the solvent effects on the reaction (Table 2).
t
The reaction of BuCl with PhSeSePh in common organic solvents
including benzene, toluene, THF, and CH3CN at ambient temperature
and boiling temperature of the solvents gave the product 1 in low to
moderate yields. At room temperature, chlorinated solvents such as
CH2Cl2 (Table 1, entry 2) and ClCH2CH2Cl (Table 2, entry 4) were
optimal. However, the yield of the product 1 decreased dramatically
at the boiling temperature of ClCH2CH2Cl (entry 4). We thought that
it might be related with the thermal stability of the product 1. In
controlled experiments, it was found that the reaction in CH2Cl2 was
completed within 3 h at room temperature and in 1 h at reflux giving
quantitative yields of the product. On the other hand, when the
reaction time increased to 24 h in both cases, it caused a decrease in
the yield of the product to 80% and 70%, respectively. Thus, it proved
that the prolonged reaction time gave a detrimental effect on the
yield of the product. We also carried out the reaction in aqueous
CH2Cl2 to afford a low yield of the product (entry 6). Notably, CH2Cl2
was the solvent of choice.
9
6
NR
C6H11
Br
10
11
PhCH2Br
7f
8g
86 (70)
98 (85)
Br
Br
Br
12
13
14
9
99 (95)
- (84)
- (52)
Br
PhCH2Cl
7f
Cl
10d
MeO
Cl
15
11d
67 (59)
Under optimal reaction conditions, a variety of sterically
diverse organic halides brought into the reaction with diphenyl
12b
12b
13d
99 (89)
97 (73)
40 (32)
I
16
17
18
Br
Br
Ph
Table 2
t
Solvent effects on the reaction of BuCl with PhSeSePh in the presence of indium
19
20
PhBr
PhI
14h
14h
NR
NR
In (1 equiv)
solvent
t
1
+
Bu Cl
PhSeSePh
(1 equiv)
(2 equiv)
21
15i
85
Br
Entry
Solvent
Yielda,c (%)
Yieldb,c (%)
Br
1
2
3
4
5
6
Benzene
Toluene
THF
ClCH2CH2Cl
CH3CN
51
38
0
99
50
d
65
41
22
52
66
42
a
The reaction was analyzed by GC, and the yield was calculated on the base of the
amount of RX. The yields in parentheses are isolated yields.
b
Ref. 4m.
Ref. 11.
Ref. 4g.
Ref. 13.
Ref. 4g.
Ref. 12.
Ref. 4a.
Ref. 4f.
c
d
CH2Cl2/H2O (9:1, v/v)
e
a
f
The reaction was carried out at room temperature for 3 h.
The reaction was carried out in a boiling solvent for 1 h.
The reaction was analyzed by GC, and the yield was calculated on the base of the
b
c
g
h
t
i
amount of BuCl.

W. Munbunjong et al. / Tetrahedron 65 (2009) 2467–2471
2469
Table 5
ring, the position of the substituent did not affect the yield of the
products. Therefore, p- and o-bromobenzyl phenyl selenides (8 and
9) were afforded in 98% and 99% yields, respectively (entries 11 and
12). On the other hand, p-methoxybenzyl chloride was converted
into the selenide 10 in moderate yield (entry 14). The reaction was
then attempted with allyl halides, which were transformed into
allyl phenyl selenide (12) in excellent yields (entries 16 and 17).
Cinnamyl bromide was converted to cinnamyl phenyl selenide (13)
in 32% isolated yield along with the by-product of rearrangement
(entry 18). Aryl halides turned out to be inactive under the present
reaction conditions (entries 19 and 20). The substitution reaction of
a dibromo substrate took place selectively at the tertiary carbon
center (entry 21). These findings led us to conclude that the
consecutive order of reactivity of alkyl halides is tert-alkyl, allyl,
benzyl[secondary and primary alkyl halides.
Synthesis of primary and secondary alkyl phenyl selenides with indium in the
presence of a catalytic amount of iodine
In (1 equiv), I2
R
SePh
R
X
+
PhSeSePh
(1 equiv)
CH2Cl2, reflux
(2 equiv)
Entry
RX
iPrI
I2 (equiv)
Time (h)
RSePh
Yielda (%)
1
2
3
4
5
6
7
8
9
10
0.2
0.5
0.2
0.5
0.5
0.2
0.5
0.2
0.5
0.5
1
4
2.5
7
4
3
7
7
7
3b
98 (70)
90 (82)
96 (81)
NR
96 (88)
99 (78)
85 (74)
99 (85)
NR
Cyclohexyl bromide
Bornyl iodide
2-Chloroadamantane
CH3(CH2)5I
4b
16b
17
5c
CH3(CH2)11
I
18d
5c
CH3(CH2)5Br
CH3(CH2)11Br
PhCH2CH2Cl
CH3(CH2)19Cl
18d
19
20
7
NR
It has been reported that the reactions using metal have been
promoted by the addition of iodine.4m,8 We thought that the
addition of iodine might increase the yields of the desired products
under the present reaction conditions. When 1.0 equiv of PhSeSePh
a
The reaction was analyzed by GC, and the yield was calculated on the base of the
amount of RX. The yields in parentheses are isolated yields.
b
Ref. 4g.
Ref. 13.
Ref. 4m.
c
t
was allowed to react with 2.0 equiv of BuCl in the presence of
d
indium (1.0 equiv) in benzene at room temperature for 3 h, the
product 1 was obtained in 51% yield (Table 4, entry 1). When
0.2 equiv of iodine was added, the yield improved somewhat (entry
2). However, in boiling benzene, the addition of a catalytic amount
of iodine (0.2 equiv) to the reaction caused a tremendous increase
in the yield of the product 1 to a quantitative yield compared with
the case in which iodine was absent (entries 3 and 4).
We thought that these reaction conditions might be applicable
to the preparation of primary and secondary alkyl phenyl selenides,
which were obtained in very low yields without iodine (Table 3,
entries 6–9). Various primary and secondary alkyl halides were
allowed to react under the reaction conditions, and the results are
shown in Table 5. Secondary alkyl iodides and bromides (entries 1
and 2), and primary alkyl iodides and bromides (entries 5–8) were
highly effective to In/I2 promoted selenation. It was interesting to
note that sterically congested iodide, bornyl iodide, proceeded
efficiently affording the corresponding alkyl phenyl selenide 16 in
high yield (entry 3). In general, alkyl iodides were more reactive
than alkyl bromides. In the case of secondary alkyl chlorides such as
2-chloroadamantane, the reaction did not proceed (entry 4). Fur-
thermore, the reaction of primary alkyl chlorides did not proceed
under the same reaction conditions (entries 9 and 10). Addition of
iodine to the reaction enhanced the rate of reaction.
allyl phenyl sulfide (24) was produced in 40% isolated yield (entry
8). Primary and secondary alkyl iodides were practically inactive
under the present reaction conditions even in the presence of
iodine (entries 9 and 10).
In an effort to extend the scope of our newly developed system,
we carried out the reaction of a wide range of structurally diverse
acid chlorides with diphenyl diselenide to produce the corre-
sponding acyl phenyl selenides, and the results are presented in
Table 7. Treatment of benzoyl chloride (2.0 equiv) with PhSeSePh
(1.0 equiv) in CH2Cl2 in the presence of indium (1.0 equiv) at reflux
for 1 h furnished benzoyl phenyl selenide (27) in 62% yield (entry
1). The yield of 27 was improved to 92% yield by employing
1.5 equiv of indium (entry 2). p-Methoxy (28) and p-bromobenzoyl
(29) phenyl selenides were also obtained in high yields (entries 3
and 4). However, benzoic acid chlorides with nitro group at o- or
p-position were not active substrates under the same reaction
conditions giving low yields of the corresponding acyl phenyl
selenides (30 and 31) even though they were allowed to react for
prolonged time (entries 5 and 6). A heterocyclic acid chloride,
2-thiophenecarbonyl chloride, produced 2-thiophenecarbonyl
Next, we applied the method to the preparation of alkyl phenyl
sulfides. Various alkyl phenyl sulfides were prepared, and the
results are summarized in Table 6. Generally, the formation of
sulfides took longer reaction time than the formation of selenides.
The reactions with tertiary alkyl halides were completed within
3–5 h without difficulty (entries 1–5). The transformation of benzyl
bromide and chloride to benzyl phenyl sulfide (23) could also be
accomplished giving high yields (entries 6 and 7). With allyl iodide,
Table 6
Synthesis of alkyl phenyl sulfides from alkyl halides
In (1 equiv)
R
SPh
+
PhSSPh
(1 equiv)
R
X
CH2Cl2, reflux
(2 equiv)
Entry
RX
RSPh
Time (h)
Yielda (%)
1
2
3
4
5
6
7
8
9
10
tBuI
21c
21c
21c
22d
22d
23e
23e
24f
25f
26g
1
3
5
3
3
3
3
6
8
99 (89)
96 (85)
80 (72)
80
65 (58)
88 (86)
80
- (40)
- (10)b
- (10)b
tBuBr
tBuCl
1-Iodoadamantane
1-Bromoadamantane
PhCH2Br
Table 4
t
Effects of the amount of iodine on the reaction of BuCl with PhSeSePh
In (1 equiv), l2
benzene
PhCH2Cl
t
1
+
Bu Cl
PhSeSePh
(1 equiv)
CH2]CHCH2I
iPrI
(2 equiv)
CH3(CH2)11
I
21
a
The reaction was analyzed by GC, and the yield was calculated on the base of the
amount of RX. The yields in parentheses are isolated yields.
Entry
I2 (equiv)
Temp
Time (h)
Yielda (%)
1
2
3
4
0
0.2
0
rt
rt
Reflux
Reflux
3
1
1
0.5
51
76
65
99
b
I2 (0.2 equiv) was added.
Ref. 4m.
Ref. 14.
Ref. 15.
c
d
0.2
e
f
a
Refs. 16 and 17.
The reaction was analyzed by GC, and the yield was calculated on the base of the
g
t
Ref. 4c.
amount of BuCl.

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W. Munbunjong et al. / Tetrahedron 65 (2009) 2467–2471
Table 7
reacts with a nucleophilic phenyl selenide to produce alkyl phenyl
Synthesis of acyl phenyl selenides from acid chlorides
selenide via SN1 pathway. In the presence of iodine, the reactivity
of the reaction depends mainly on the leaving group of substrates.
The reaction with primary alkyl iodides or bromides proceeded
efficiently while the reaction with primary alkyl chlorides did not
take place. Indium species, In(SePh)3, may react with iodine, and
then it cannot coordinate with the substrate. Thus, it is possible that
the nucleophilic phenyl selenide can approach from the backside of
the substrate, and the reaction proceeds via SN2 pathway. Scheme 2
illustrates the plausible mechanism for the reaction of alkyl halides
with diphenyl diselenide in the presence of indium.
O
C Cl
O
C
In (1.5 equiv)
+
PhSeSePh
(1 equiv)
R
R
SePh
CH2Cl2, reflux
(2 equiv)
Entry
RC(O)Cl
Time (h)
RC(O)SePh
Yielda (%)
1
2
3
4
5
6
PhC(O)Cl
PhC(O)Cl
(p-OMe)C6H4C(O)Cl
(p-Br)C6H4C(O)Cl
(p-NO2)C6H4C(O)Cl
(m-NO2)C6H4C(O)Cl
2
2
1.5
1.5
24
24
27c
27c
28c
29d
30c
31
62b
92
80
88
20
10
2 In(SePh)3
2 In + 3 PhSeSePh
+
O
7
8
1.5
1.5
32c
33
90
55
S
Cl
O
+
In(SePh)3
3 RX
3 RSePh
InX3
Scheme 2.
O
Cl
9
10
11
CH3(CH2)2C(O)Cl
(CH3)2CHC(O)Cl
C6H11C(O)Cl
1.5
2
3
34c
35c
36e
80
92
62
3. Conclusions
In summary, an efficient and practical one-pot process was
developed for synthesizing alkyl phenyl selenides, sulfides,
selenoesters by using indium metal. The reaction showed the
selectivity for tert-alkyl, benzylic, and allylic halides over primary
and secondary alkyl halides. In these applied reactions appending
iodine, the primary and secondary alkyl phenyl selenides were
obtained in high yields with the exception of primary and
secondary alkyl chlorides. The trend in the reactivity of the sub-
strates under the present reaction conditions differs from the
reaction in which metal phenyl selenolates are generated by other
metals or bases. The novel method has the advantages of a simple
experimental procedure, mild and neutral reaction conditions, and
high yields of the desired products.
O
12
2
37
59
65
Cl
13
tBuC(O)Cl
1.5
38c
a
The yield was calculated on the base of the amount of RC(O)Cl.
In (1.0 equiv) was used.
Ref. 4k.
b
c
d
e
Ref. 18.
Ref. 19.
phenyl selenide (32) in excellent yield (entry 7) under the present
reaction conditions, while 2-furoyl phenyl selenide (33) was
obtained by the reaction of 2-furoyl chloride in moderate yield
(entry 8). In addition, aliphatic acid chlorides gave high yields of
acyl phenyl selenides, 34 and 35 (entries 9 and 10). On the other
hand, the aliphatic acid chlorides, which were sterically hindered
proved to be less reactive substrates to the present method (entries
11–13).
4. Experimental section
4.1. General
All solvents were dried by standard methods. Unless otherwise
specified, chemicals were purchased from commercial suppliers
and used without further purification. Column chromatography
was performed on silica gel (230–400 mesh, Merck). TLC was
performed on glass sheets pre-coated with silica gel (Kieselgel 60
PF254, Merck). Melting points were determined with a Fisher-Johns
melting point apparatus and are uncorrected. The 1H and 13C NMR
spectra were performed on a Bruker 400 NMR spectrometer, which
operated at 400 MHz for 1H and 100 MHz for 13C nuclei and are
internally referenced to residual protio solvent signals. Chemical
shifts are reported in parts per million (ppm). IR spectra were
Compared with primary alkyl halides, tertiary alkyl halides
showed a higher reactivity under the present reaction conditions
(Table 2). This trend in the reactivity of the substrates is in the line
of radical or carbocation intermediates. We carried out some
competitive experiments with mixtures of tertiary alkyl halides. A
set of mixture of tert-butyl halides was treated with indium metal
in CH2Cl2 at reflux for 15 min. The resulting mixtures were
analyzed. The ratio of the remaining tert-butyl halides as Cl/I, Cl/Br,
and Br/I was 6.5:1, 3.6:1, and 2.6:1, respectively. Thus, the relative
reactivity of halides was found to follow the sequence of I>Br>Cl. It
is consistent with the order of halides with respect to the reactivity
under radical reaction conditions. To prove whether the reaction
recorded on
a Perkin–Elmer 16 PC FTIR spectrometer. Gas
chromatography analyses were carried out on a Shimadzu gas
chromatograph GC-14A instrument equipped with a flame ioniza-
tion detector (FID) using nitrogen as a carrier gas. The column
used for chromatography was a capillary column type HP-5
(30 mꢀ250 mm) from Hewlett–Packard. Gas chromatography–
mass spectrometry analyses were carried out on an Agilent
Technologies G1530N instrument (6890N Network GC system-
5973 mass selective detector, EI, 70 eV). Microanalyses were per-
formed on a CE instrument EA1110 elemental analyzer.
occurs via
a free radical pathway, a controlled reaction of
1-iodoadamantane was performed in the presence of galvinoxyl
free redical.9 The efficiency of the reaction was the same as that of
the reaction performed without the radical scavenger. In addition,
no dimerization product was found in the reaction of PhSeSePh
with an alkyl halide. On the basis of these results, the free radical
pathway might be excluded. The reactivity of tertiary alkyl,
benzylic, and allylic halides is higher than that of primary and
secondary alkyl halides. In addition, the reactions of aromatic acid
halides with an electron-withdrawing group were sluggish. These
facts imply that in the case of alkyl halides, which can generate
a stable carbocation, an electron-deficient intermediate is produced
during the reaction. Thus, indium metal first reacts with an alkyl
halide to generate In(SePh)3,10 which may coordinate to a substrate
and produce a carbocation-like intermediate. The intermediate
4.2. General procedure for the synthesis of alkyl phenyl
selenides and sulfides
A mixture of indium powder (57.4 mg, 0.5 mmol), diphenyl
diselenide or diphenyl disulfide (0.5 mmol), and an organic halide

W. Munbunjong et al. / Tetrahedron 65 (2009) 2467–2471
2471
(1.0 mmol) in CH2Cl2 (5 mL) was stirred at reflux for 1 h under
References and notes
nitrogen. The mixture was then quenched with 1 M HCl and
extracted with ether. The organic layer was washed with brine,
dried over MgSO4, and purified by column chromatography on
silica gel to give the corresponding alkyl phenyl selenide.
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mon: Oxford, 1986; (j) Patai, S.; Rappoport, Z. The Chemistry of Organic Selenium
and Tellurium Compounds; Wiley & Sons: New York, NY, 1986; Vols. 1 and 2; (k)
Nicolaou, K. C.; Petasis, N. A. Selenium in Natural Products Synthesis; CIS:
Pennsylvania, PA, 1984; (l) Liotta, D. Acc. Chem. Res. 1984, 17, 28.
4.2.1. o-Bromobenzyl phenyl selenide (9)
Pale yellow oil. Rf 0.25 (hexane); 1H NMR (CDCl3)
d 4.19 (s, 2H),
7.01–7.08 (m, 3H), 7.22–7.29 (m, 3H), 7.47–7.49 (m, 2H), 7.54 (d, 1H,
J¼7.7 Hz); 13C NMR (CDCl3)
d 33.0, 124.4, 127.3, 127.7, 128.5, 129.0,
130.6, 133.1, 134.5, 138.3. Anal. Calcd for C13H11BrSe: C, 47.88; H,
3.40. Found: C, 47.90; H, 3.37.
4.3. General procedure for the synthesis of acyl phenyl
selenides
Indium powder (86.1 mg, 0.75 mmol), diphenyl diselenide
(156.1 mg, 0.5 mmol), and CH2Cl2 (2 mL) were placed in a two-
necked flask. An acid chloride (1.0 mmol) in CH2Cl2 (1 mL) was
added to the mixture, and the resulting mixture was stirred at
reflux for 1 h under argon. The mixture was then quenched with
1 M HCl and extracted with CH2Cl2. The organic layer was washed
with brine and dried over MgSO4. After evaporation, the residue
was purified by column chromatography on silica gel to give the
corresponding acyl phenyl selenide.
3. For selected reviews: (a) Miyaura, N. In Metal-Catalyzed Cross-Coupling
Reactions; Meijere, A., Diederich, F., Eds.; Wiley-VCH: Weinheim, 2004; Vol. 1,
pp 41–123; (b) Krief, A. In Comprehensive Organometallic Chemistry II; Abel, E.
W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, NY, 1995; Vol. 11,
Chapter 13; (c) Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.;
Pergamon: New York, NY, 1991; Vol. 4.
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Ranu, B. C.; Chattopadhyay, K.; Banerjee, S. J. Org. Chem. 2006, 71, 423; (c) Ajiki,
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poor, M. Synlett 2005, 121; (e) Zhao, X.; Yu, Z.; Yan, S.; Wu, S.; Liu, R.; He, W.;
Wang, L. J. Org. Chem. 2005, 70, 7338; (f) Krief, A.; Derock, M.; Lacroix, D. Synlett
2005, 2832; (g) Ranu, B. C.; Mandal, T. J. Org. Chem. 2004, 69, 5793; (h) Cohen,
R. J.; Fox, D. L.; Salvatore, R. N. J. Org. Chem. 2004, 69, 4265; (i) Taniguchi, N.;
Onami, T. J. Org. Chem. 2004, 69, 915; (j) Beletskaya, I. P.; Sigeev, A. S.;
Peregudov, A. S.; Petrovskii, P. V. Tetrahedron Lett. 2003, 44, 7039; (k) Nish-
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5495; (o) Bieber, L. W.; de Sa´, A. C. P. F.; Menezes, P. H.; Gonçalves, S. M. C.
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4.3.1. m-Nitrobenzoyl phenyl selenide (31)
Pale yellow solid. Mp 109–111 ꢁC (hexane/EtOAc); Rf 0.23 (hex-
ane/EtOAc, 9:1); IR (KBr) 3070, 2922, 1680, 1536, 1439, 1346, 1194,
1089, 925, 844 cmꢂ1
;
1H NMR (CDCl3)
d
7.43–7.67 (m, 5H), 7.71
(t, 1H, J¼8.0 Hz), 8.24 (d, 1H, J¼7.7 Hz), 8.48 (d, 1H, J¼8.0 Hz), 8.77
(s, 1H); 13C NMR (CDCl3)
122.2, 124.9, 128.0, 129.6, 129.6, 130.2,
d
132.6, 136.2, 139.9, 148.5, 191.9; MS m/z (relative intensity) 307
(Mþ), 207, 157, 150, 104, 92, 76, 65, 50. Anal. Calcd for C13H9NO3Se:
C, 51.00; H, 2.96; N, 4.57. Found: C, 51.00; H, 2.95; N, 4.50.
´
5. For reviews: (a) Auge, J.; Lubin-Germain, N.; Uziel, J. Synthesis 2007, 1739; (b)
Nair, V.; Ros, S.; Jayan, C. N.; Pillia, B. S. Tetrahedron 2004, 60, 1959; (c) Podlech,
J.; Maier, T. C. Synlett 2003, 633; (d) Li, C.-J.; Chan, T.-H. Tetrahedron 1999, 55,
11149; (e) Li, C.-J. Tetrahedron 1996, 52, 5643; (f) Cintas, P. Synlett 1995, 1087;
(g) Lubineau, R.; Ange´, J.; Queneau, Y. Synthesis 1994, 741; (h) Li, C.-J. Chem. Rev.
1993, 93, 2023.
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Chem. Soc. 2003, 24, 155; (e) Jang, D. O.; Cho, D. H. Synlett 2002, 631.
7. Munbunjong, W.; Lee, E. H.; Chavasiri, W.; Jang, D. O. Tetrahedron Lett. 2005, 46,
8769.
4.3.2. 2-Furoyl phenyl selenide (33)
Pale yellow oil. Rf 0.26 (hexane/EtOAc, 95:5); IR (neat) 3136,
3050, 1766, 1657, 1556, 1454, 1377, 1248, 1151, 1023, 945, 816 cmꢂ1
;
1H NMR (CDCl3)
J¼3.5 Hz), 7.38–7.48 (m, 3H), 7.57 (d, 1H, J¼3.7 Hz), 7.65 (m, 2H);
d
6.59 (dd, 1H, J¼3.6, 1.6 Hz), 7.22 (d, 1H,
13C NMR (CDCl3)
d 112.9, 115.4, 124.8, 129.2, 129.4, 136.4, 146.8,
151.7, 180.8; MS m/z (relative intensity) 252 (Mþ), 157, 154, 115, 95,
77, 67, 51. Anal. Calcd for C11H8O2Se: C, 52.61; H, 3.21. Found: C,
52.64; H, 3.19.
8. (a) Nishino, T.; Watanabe, T.; Okada, M.; Nishiyama, Y.; Sonoda, N. J. Org. Chem.
2002, 67, 966; (b) Mashima, K.; Nakayama, Y.; Fukumoto, H.; Kanehisa, N.; Kai,
Y.; Nakamura, A. J. Chem. Soc., Chem. Commun. 1994, 2523.
4.3.3. 1-Adamantanecarbonyl phenyl selenide (37)
9. (a) Takami, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2004, 6, 4555; (b) Uhl, W.
Phosphorus, Sulfur Silicon Relat. Elem. 2004, 179, 743; (c) Miyabe, H.; Naito, T.
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2417; (e) Yanada, R.; Obika, S.; Nishimori, N.; Yamauchi, M.; Takemoto, Y.
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11. Perkins, M. J.; Turner, E. S. J. Chem. Soc., Chem. Commun. 1981, 139.
12. Higuchi, H.; Otsubo, T.; Ogura, F.; Yamaguchi, H.; Sakata, Y.; Misumi, S. Bull.
Chem. Soc. Jpn. 1982, 55, 182.
Pale yellow solid. Mp 51–53 ꢁC (hexane/EtOAc); Rf 0.29 (hexane/
EtOAc, 9:1); IR (neat) 3070, 2906, 2852,1715,1575, 1451, 1342,1260,
1124, 980, 902 cmꢂ1; 1H NMR (CDCl3)
d
1.58 (s, 6H),1.99 (s, 6H), 2.09
(s, 3H), 7.32–7.53 (m, 5H); 13C NMR (CDCl3)
d
25.8, 27.8, 35.1, 37.6,
37.8, 129.0, 129.5, 131.0, 135.2, 185.0; MS m/z (relative intensity) 163
(MþꢂPhSe), 157, 135, 107, 93, 79, 55. Anal. Calcd for C17H20OSe:
C, 63.95; H, 6.31; O, 5.01; Se, 24.73. Found: C, 63.91; H, 6.28.
13. Mueller, P.; Nguyen, T. M. P. Helv. Chim. Acta 1980, 63, 2168.
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Acknowledgements
This work was supported by the Center for Bioactive Molecular
Hybrids and Yonsei University. W.M. is thankful to Thailand
Research Fund for the 2004 Royal Golden Jubilee Ph.D. research
assistant fellowship.
19. Boger, D. L.; Mathvink, R. J. J. Org. Chem. 1989, 54, 1777.