An efficient and general procedure for the synthesis of alkynyl chalcogenides (selenides and tellurides) by alumina-supported Cu(II)-catalyzed reaction of alkynyl bromides and diphenyl dichalcogenides

Article abstract of DOI:10.1016/j.tet.2012.08.046

Alumina (Al₂O₃) supported Cu(II) efficiently catalyzes the reaction of alkynyl bromides and diphenyl diselenides and ditellurides in presence of Zn dust or indium(I) bromide to provide the corresponding alkynyl selenides and tellurides. The reactions of a wide variety of substituted alkynyl bromides have been addressed. The zinc dust or InBr is required for the cleavage of diphenyl selenides/tellurides. The mechanism of the reaction is established. The yields of products are high and the catalyst is recycled.

Full text of DOI:10.1016/j.tet.2012.08.046

Tetrahedron 68 (2012) 10542e10549
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An efficient and general procedure for the synthesis of alkynyl chalcogenides
(selenides and tellurides) by alumina-supported Cu(II)-catalyzed reaction of
alkynyl bromides and diphenyl dichalcogenides
,
Sabir Ahammed a, Sukalyan Bhadra a, Debasish Kundu a, Bojja Sreedhar b, Brindaban C. Ranu a
*
a Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, India
b Inorganic Chemistry Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 25 June 2012
Received in revised form 14 August 2012
Accepted 16 August 2012
Available online 6 September 2012
Alumina (Al2O3) supported Cu(II) efficiently catalyzes the reaction of alkynyl bromides and diphenyl
diselenides and ditellurides in presence of Zn dust or indium(I) bromide to provide the corresponding
alkynyl selenides and tellurides. The reactions of a wide variety of substituted alkynyl bromides have
been addressed. The zinc dust or InBr is required for the cleavage of diphenyl selenides/tellurides. The
mechanism of the reaction is established. The yields of products are high and the catalyst is recycled.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Alkynyl selenide
Alkynyl telluride
Heterogeneous catalysis
Alumina
Copper(II)
1. Introduction
However, this method has serious limitations with sensitive func-
tionalities using a strong base and this limits the scope of the re-
The organochalcogenides, in general, have received considerable
attention in recent times because of their potential applications in
organic synthesis and as useful materials.1 The alkynyl chalcogen-
ides, particularly tellurides have been studied less compared to other
derivatives although these compounds are of much use as versatile
intermediates for a variety of reactions, such as hydrohalogenation,2
hydroamination,3 hydroboration,4 hydrosulfonation,5 among oth-
ers.6e8 They have also been used as important dienophiles in cy-
cloaddition reactions.9 In addition, they, especially tellurides have
attracted recent interest for medical applications.10 Thus de-
velopment of efficient methods for these useful compounds is of
considerable interest. From literature search we found that only
a limited number of methods have been reported for alkynyl
chalcogenides11e16 and interestingly these methods addressed pri-
marily selenides and alkynyl tellurides are rarely exemplified12e15
despite their immense importance.10 Thus our aim is to develop
a general procedure for selenides as well as tellurides. The classical
approach utilized the high acidity of terminal acetylenic CeH bond
to form alkynyl metal derivative by treatment with strong organo-
metallic bases and subsequent reaction with elemental chalcogen.11
action. In recent years two protocols received attention. One involves
the reaction of terminal alkynes with diphenyl dichalcogenides in
presence of a base, CuI and/or Lewis acid.12,13 The other one includes
the reaction of alkynyl bromides with diphenyl dichalcogenides in
presence of CuI and ligand.14,15 The selenodecarboxylation of aryl
propiolic acid with diorganodiselenide promoted by iodosobenzene
diacetate made a different approach for the synthesis of alkynyl
selenides.16 Most of these methods used costly reagents like CuI,
which was not recyclable and focused only on alkynyl selenides. We
report here a general procedure for the synthesis of alkynyl selenides
as well as tellurides by a simple reaction of alkynyl bromides and
diphenyl diselenides/ditellurides catalyzed by alumina-supported
Cu(II) (Cu/Al2O3), a unique reagent recently developed by our
group (Scheme 1).17
2. Results and discussion
To standardize the reaction conditions a series of experiments
were performed under varying reaction parameters, such as sol-
vent, time, temperature and additive (Zn/InBr) for a representative
reaction of phenyl acetylene bromide and diphenyl diselenide/tel-
luride. The results are summarized in Table 1. It was found that
reaction with diphenyl diselenide proceeded efficiently in presence
* Corresponding author. Fax: þ91 33 24732805; e-mail address: ocbcr@iacs.res.in
(B.C. Ranu).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.08.046

S. Ahammed et al. / Tetrahedron 68 (2012) 10542e10549
10543
Ph2Te2
R2Se2
Cu/Al2O3 (4 mol%)
Cu/Al2O3 (4 mol%)
Ar
Te Ph
Ar
Br
Ar
Se R
InBr, 14-22 h
110 oC, DMF
Zn, 7-9 h
70 oC, THF
Scheme 1. Synthesis of alkynyl selenides and tellurides.
of zinc dust in THF at 70 ꢀC being complete by 8 h (Table 1, entry 6,
highlighted in bold as best condition). THF was found to be best
among other solvents studied. However the reaction with diphenyl
ditelluride did not go well with zinc dust giving only 12% yield of
product even after heating for 24 h. Replacement of zinc by InBr,18
another additive, proved successful. Best result in terms of yield
(81%) was obtained when the reaction was carried out in DMF at
110 ꢀC for 16 h (Table 1, entry 14, highlighted in bold as best con-
dition). Interestingly, THF, which was found to be best in selenide
reaction, did not work at all in telluride reaction. H2O was found to
be useless in both the reactions. None of these reactions occurred at
room temperature. The selenylation in absence of Zn and tellur-
ylation without InBr did not initiate at all. The amount of the cat-
alyst was optimized to 4 mol % for best results.
In a typical experimental procedure, a mixture of alkynyl bro-
mide and diphenyl diselenide was heated at 70 ꢀC inTHF in presence
of zinc powder and Cu/Al2O3 for a certain period of time (TLC).
Standard work-up and purification by column chromatography
provided the product. The same procedure was followed for alkynyl
tellurides with replacement of Zn powder by InBr and using DMF in
place of THF.
Table 1
Standardization of reaction conditions
Cu/Al2O3 (4 mol%)
Ph
Br Ph2Y2
+
Ph
Y
Ph
additive (X) (0.5 mmol),
time, temp., solvent
Entry
Y
X
Solvent
Time (h)
Temp (ꢀC)
Yielda (%)
1
2
Se
Se
Se
Se
Se
Se
Se
Te
Te
Te
Te
Te
Te
Te
Te
Te
Te
Zn
Zn
Zn
Zn
Zn
Zn
Zn
Zn
Toluene
DMF
DMSO
THF
H2O
THF
THF
THF
DMF
DMSO
Toluene
THF
12
16
12
12
12
8
110
110
100
70
110
70
14
73
76
d
d
92
d
d
12
72
17
d
d
81
23
36
d
3
4b
5
6
7
8
9
10
11
12
13
14
15b
16
17
8
8
rt
70
Zn
24
16
16
16
16
16
12
12
12
110
110
110
70
100
110
70
InBr
InBr
InBr
InBr
InBr
InBr
InBr
InBr
H2O
DMF
DMF
DMF
DMF
70
rt
A series of diversely substituted alkyl, aryl and heteroaryl al-
kynes were subjected to reaction with diaryl diselenides by this
procedure to produce the corresponding alkynyl selenides. The
results were reported in Table 2. Significantly, alkyl-, aryl- and
heteroaryl-substituted alkynes gave uniform results in terms of
a
Yields refer to those of pure products characterized by IR, 1H NMR and 13C NMR
spectroscopic data.
b
Reaction carried out without catalyst.
Table 2
Synthesis of alkynyl selenides
Cu/Al2O3
R2SeSeR2
R1
Br
R1
Se
R2
+
Zn dust, 7-9 h
THF, Reflux
Entry
1
R1
R2
Time (h)
8
Product
Yielda (%)
83
Se
n-Hexyl
Ph
4
2
3
Ph
Ph
Ph
8
8
92
88
Se
p-MeC6H4
Se
Se
4
o-MeC6H4
Ph
9
83
5
6
7
p-EtC6H4
Ph
Ph
Ph
8
8
8
90
89
Se
Et
MeO
Br
p-OMeC6H4
p-BrC6H4
Se
87
Se
(continued on next page)

10544
S. Ahammed et al. / Tetrahedron 68 (2012) 10542e10549
Table 2 (continued )
Entry
R1
R2
Time (h)
Product
Yielda (%)
Se
8
m-FC6H4
Ph
7
89
F
9
p-CIC6H4
Ph
Ph
7
86
91
85
83
Cl
Se
10
11
12
p-nPentylC6H4
8
C5H11
Se
Ph
Ph
p-OMeC6H4
p-MeC6H4
8
8
Se
OMe
Se
13
1-Naphthyl
Ph
8
86
Se
Se
14
15
6-Methoxy-2-naphthyl
2-Thienyl
Ph
Ph
9
7
81
91
MeO
Se
S
16
17
Biphenyl
Ph
Ph
8
8
89
86
Se
p-CIC6H4
Se
Cl
F
Se
18
Ph
Ph
m-FC6H4
8
8
78
88
19
Me
Se
a
Yields refer to those of pure products characterized by IR, 1H NMR and 13C NMR spectroscopic data.
yield and reaction time. The reaction with both electron donating
(Table 2, entries 11 and 12) and electron withdrawing (Table 2,
entries 17 and 18) groups-substituted diaryl diselenides also pro-
vided high yields. The dialkyl (methyl) diselenide too underwent
reaction with phenyl acetylene bromide without any difficulty
(Table 2, entry 19). The selenylation is highly chemoselective as
reaction occurs only at Br on alkynyl chain leaving Br on the aro-
matic ring unaffected (Table 2, entry 7). Thienyl acetylenic bromide
participates in this reaction without any difficulty and the corre-
sponding selenide may be of interest (Table 2, entry 15).
Several alkynyl bromides substituted with hexyl, substituted
phenyl, naphthyl and thiophenyl moieties participated in tellur-
ylation reaction by the procedure described earlier, to produce the
corresponding alkynyl tellurides. The results were summarized in
Table 3. The reaction proceeded uniformly irrespective of the na-
ture of alkynyl bromide.
In general, all selenylation and tellurylation reactions are clean
and high yielding. Several functionalities, such as OMe, Cl, Br, F are
well accepted in this reaction. The reactions are uniform with o-, m-
and p-substituted alkynyl bromides. The tellurylation reactions
required longer reaction period than those for selenylation. The Cu/
Al2O3 catalyst was recovered and recycled for six subsequent runs
without any appreciable loss in catalytic activity (Fig. 1). Several of
the alkynyl selenides and almost all of these tellurides are new and
not reported earlier.
To investigate the mechanism of the reaction, a series of ex-
periments were conducted. The XPS (X-ray photo electron spec-
troscopy) study of the fresh and used catalyst of the selenylation
reaction at the Cu-2p level shows the 2p3/2 lines at 934.536 and
934.585 eV, respectively, with characteristic shake up features
(Figs. 2 and 3).19 This clearly indicates that Cu is in þ2 oxidation
state before and after the reaction.

S. Ahammed et al. / Tetrahedron 68 (2012) 10542e10549
10545
Table 3
Synthesis of alkynyl tellurides
Cu/Al2O3
Ph2Te2
R
Br
+
R
Te
Ph
InBr, 16-22 h
DMF, 120 oC
Entry
1
R
Time (h)
22
Product
Yielda (%)
n-C6H13
75
81
Te
5
2
3
Ph
16
18
Te
Te
o-MeC6H4
78
4
5
6
7
p-EtC6H4
p-OMeC6H4
p-BrC6H4
p-CIC6H4
18
16
21
19
81
83
85
87
Te
Et
MeO
Br
Te
Te
Te
Cl
Te
8
9
6-Methoxy-2-naphthyl
14
76
MeO
Te
2-Thienyl
Biphenyl
16
21
82
83
S
10
Te
a
Yields refer to those of pure products characterized by IR, 1H NMR and 13C NMR spectroscopic data.
100
80
60
40
20
0
0
1
2
3
4
5
6
7
No. of Cycle
Fig. 1. Recyclability of catalyst.
Fig. 2. XPS of Cu 2p3/2 for fresh catalyst.

10546
S. Ahammed et al. / Tetrahedron 68 (2012) 10542e10549
additional band at 2800e3200 cmꢁ1 corresponding to the aro-
matic CeH stretching frequencies indicating the addition of PhSe
moiety to Cu(II) centre (Fig. 4). The formation of this type of
complex is also not unprecedented.20,21 The XPS study of this
complex A shows Cu 2p3/2 and Se 3d lines at 934.448 and
53.277 eV, respectively (Figs. 5 and 6). This also suggests Cu(II)eSe
bond formation. The tellurylation reaction also proceeds through
the same mechanism as XPS analysis study of the intermediate
complex and recovered Cu catalyst showed similar characteristic
peaks (Figs. 7 and 8).
Fig. 3. XPS of Cu 2p3/2 for regenerated Cu/Al2O3 catalyst.
Thus, we propose that the reaction proceeds through a Cu(II)
assisted nucleophilic displacement process. In the first step Zn
interacts with Ph2Se2 to form (PhSe)2Zn, which transfers the
PhSe moiety to Cu(II) catalyst to form intermediate A. This in-
termediate then combines with alkynyl bromide to generate
a complex B, which produces the product, selenide through
a transient intermediate C with regeneration of Cu(II) catalyst
(Scheme 2).
Fig. 4. FT-IR spectrum of intermediate A.
1/2Ph2Se2 + 1/2Zn
O
Ar
Se Ph
1/2(PhSe)2Zn
1/2Zn(II)
O
O
Cu
O
O
O
Ph
O
O
O
Se
Ar
O
SePh
O
Cu
Cu
O
O
O
O
O
C
A
Ar
Br
Fig. 5. XPS of Cu 2p3/2 for A.
1/2 ZnBr2
1/2
Ph
3. Conclusion
(II)Zn
Br
Ar
O
Se
O
Cu
In conclusion, we have developed a very efficient and general
procedure for the synthesis of alkynyl selenides and tellurides by
reaction of alkynyl bromides and diphenyl diselenides and ditel-
lurides catalyzed by heterogeneous Cu(II)/Al2O3 catalyst in pres-
ence of zinc and InBr, respectively. The attractive features of this
protocol are involvement of hitherto unexplored Cu(II) as catalyst,
general applicability to both selenide and tellurides, easy avail-
ability and recyclability of the catalyst. Significantly, this procedure
provides an easy access to a library of alkynyl selenides and tellu-
rides including alkyl as well as aryl moieties with a scope of
functionalization, which was not addressed in the existing
methods.12e15
O
O
O
B
Scheme 2. Plausible mechanism for synthesis of alkynyl selenide.
To get further evidence in support of Cu(II)-assisted nucleo-
philic displacement mechanism, when Ph2Se2 was stirred with
Cu/Al2O3 in THF in presence of Zn at 70 ꢀC for 12 h a dirty white
complex A was obtained. The FTIR of this complex shows an

S. Ahammed et al. / Tetrahedron 68 (2012) 10542e10549
10547
Fig. 6. Se 3d peaks of intermediate A.
Fig. 8. XPS of Cu 2p3/2 for regenerated Cu/Al2O3 catalyst for tellurylation.
Aldrich and used without further purification. The solvents are
purchased from local vendors (Process Chemicals, Kolkata, India)
and were dried by us in the laboratory. The bromo alkynes are
prepared from commercial alkynes by a reported procedure.22
4.2. General experimental procedure for the synthesis of
alkynyl selenides. Representative procedure for phenyl
(phenylethynyl)selane (Table 2, entry 2)
To a solution of 1-(2-bromoethynyl)benzene (181 mg, 1 mmol)
and diphenyl diselenide (156 mg, 0.5 mmol) in THF (4 mL), Cu/
Al2O3 (70 mg) and zinc powder (32.5 mg, 0.5 mmol) were added
and the mixture was stirred under argon at 70 ꢀC for 8 h (TLC). After
being allowed to cool, the THF was evaporated and the reaction
mixture was extracted with ethyl acetate (3ꢂ10 mL). The extract
was washed with water and brine and dried over Na2SO4. The crude
product was purified by column chromatography over silica gel
(hexane) to afford pure phenyl (2-phenylethynyl)selane as a yellow
liquid (236 mg, 92%), IR (neat): 3016, 2978, 2845, 2158, 1679, 1588,
1512, 1473 cmꢁ1
7.33e7.40 (m, 2H), 7.54e7.57 (m, 2H), 7.64e7.66 (m, 2H); 13C NMR
(CDCl3, 125 MHz) 69.4, 103.1, 123.3 (2C), 127.2 (2C), 128.7, 129.0,
; d 7.26e7.30 (m, 2H),
1H NMR (CDCl3, 500 MHz)
Fig. 7. Te 4d peaks of the corresponding tellurium intermediate.
d
129.7 (2C), 131.7, 131.9 (2C). These data are in agreement with the
4. Experimental section
reported one.15
In control experiments without catalyst or without additive
(InBr), the same procedure was followed in absence of the partic-
ular component.
This procedure was followed for all the reactions listed in Table
2. A few of these products are known compounds (Table 2, entries 2,
3, 6, 7, 9, 10, 11, 12, 13, 17 and 19) and were identified by comparison
of their spectra with those reported earlier.13,15,16,23e25 The prod-
ucts, which were not reported earlier, were characterized by their
spectroscopic data (IR, 1H NMR, 13C NMR and HRMS). These data are
provided below in order of their entries in Table 2.
4.1. General
1H NMR and 13C NMR spectra were recorded on a Bruker in-
strument at 500 and 125 MHz, respectively. The chemical shifts (d)
are reported in parts per million, using TMS as an internal standard
and CDCl3 as the solvent. HRMS were recorded on a Microtek Qtof
Micro YA263 spectrometer. IR spectra were recorded on a Shi-
madzu 8300 FTIR spectrometer. The starting materials, diphenyl
diselenide, diphenyl ditelluride and alkynes were purchased from

10548
S. Ahammed et al. / Tetrahedron 68 (2012) 10542e10549
4.2.1. Oct-1-yn-1-yl(phenyl)selane (Table 2, entry 1). Yield 83%,
4.2.8. (3-Fluorophenyl)(2-phenylethynyl)selane (Table 2, entry 18).
yellow viscous liquid, IR (neat): 2956, 2929, 2858, 2218, 1577, 1458,
Yield 78%, yellow liquid, IR (neat): 3061, 3019, 2160, 1589, 1472,
1379 cmꢁ1
;
1H NMR (CDCl3, 500 MHz)
d
0.847e0.849 (m, 1H),
1425, 1263, 1213 cmꢁ1 1H NMR (CDCl3, 500 MHz)
; d 6.97 (t,
0.89e0.93 (m, 2H), 1.08e1.10 (m, 2H), 1.17e1.24 (m, 1H), 1.28e1.31
(m, 2H), 1.32e1.38 (m, 1H), 1.42e1.48 (m, 1H), 1.54e1.63 (m, 1H),
2.11 (t, J¼7.5 Hz, 1H), 2.46 (t, J¼7.0 Hz, 1H), 7.22e7.26 (m, 1H),
7.29e7.38 (m, 2H), 7.52 (d, J¼7.5 Hz, 1H), 7.61 (d, J¼7.0 Hz, 1H); 13C
J¼8.5 Hz, 1H), 7.25e7.36 (m, 6H), 7.51e7.53 (m, 2H); 13C NMR
(CDCl3, 125 MHz)
d
68.3, 104.2, 114.2 (d, J¼21.2 Hz, 1C), 115.0, 116.1
(d, J¼25.0 Hz, 1C), 123.0, 124.3, 128.7 (2C), 128.8 (d, J¼22.5 Hz, 1C),
130.7, 131.9 (2C), 163.3 (d, J¼247.5 Hz, 1C); Anal. Calcd for C14H9FSe:
C, 66.11; H, 3.30; found: C, 66.14; H, 3.28%.
NMR (CDCl3, 125 MHz) d 14.1, 20.7, 22.6, 28.7, 31.5, 37.5, 57.6, 103.3,
126.8, 128.6, 128.7, 129.3, 136.1, 142.2; HRMS calcd for C14H18Se
(MþþH): 267.0652, found: 267.0648.
4.3. General experimental procedure for the synthesis of
alkynyl tellurides. Representative procedure for phenyl
(phenylethynyl)tellane (Table 3, entry 2)
4.2.2. Phenyl(o-tolylethynyl)selane (Table 2, entry 4). Yield 83%,
yellow liquid, IR (KBr): 3055, 2918, 2135, 1572, 1475, 1433,
1223 cmꢁ1
;
1H NMR (CDCl3, 500 MHz)
d
2.54 (s, 3H), 7.20 (t,
To a solution of 1-(2-bromoethynyl)benzene (181 mg, 1 mmol)
and diphenyl ditelluride (204 mg, 0.5 mmol) in DMF (4 mL), Cu/
Al2O3 (70 mg) and InBr (96.5 mg, 0.5 mmol) were added and the
mixture was stirred under argon at 110 ꢀC for 16 h (TLC). After being
allowed to cool, and the reaction mixture was extracted with ethyl
acetate (3ꢂ10 mL). The extract was washed with water and brine
and dried over Na2SO4. The crude product was purified by column
chromatography over silica gel (hexane) to afford pure phenyl(2-
phenylethynyl)tellane as a yellow liquid (247 mg, 81%), IR (neat):
J¼7.0 Hz, 1H), 7.27e7.32 (m, 3H), 7.36e7.39 (m, 2H), 7.53 (d,
J¼7.5 Hz, 1H), 7.66 (d, J¼6 Hz, 2H); 13C NMR (CDCl3, 125 MHz)
d
20.8, 72.8, 102.1, 123.1, 125.7, 127.1, 128.6, 129.0, 129.2 (2C), 129.3,
129.6 (2C), 132.1, 140.5; HRMS calcd for C15H12Se (Mþ): 272.0104,
found: 272.0106.
4.2.3. ((4-Ethylphenyl)ethynyl)(phenyl)selane (Table 2, entry 5).
Yield 90%, yellow viscous liquid, IR (neat): 3055, 2964, 2872, 2158,
1684, 1577, 1475 cmꢁ1
;
1H NMR (CDCl3, 500 MHz)
d
1.20 (t,
3071, 2926, 2162, 1963, 1577, 1483, 1286 cmꢁ1 1H NMR (CDCl3,
;
J¼6.5 Hz, 3H), 2.63 (q, J¼8.0 Hz, 2H), 6.69e7.16 (m, 2H), 7.21e7.25
500 MHz)
d
7.26e7.29 (m, 3H), 7.33 (t, J¼3.5 Hz, 3H), 7.47 (t, J¼6.5 Hz,
(m, 2H), 7.26e7.31 (m, 1H), 7.41 (d, J¼8.0 Hz, 2H), 7.56e7.59 (m,
2H), 7.75 (t, J¼6.5 Hz, 2H); 13C NMR (CDCl3, 125 MHz)
d 47.5, 113.3,
2H); 13C NMR (CDCl3, 125 MHz)
d
15.5, 29.0, 68.3, 103.4, 120.5, 127.2,
114.4,123.6,128.1,128.4 (2C),128.8,129.9 (2C),132.1 (2C),135.3 (2C).
In control experiments without catalyst or without additive
(InBr), the same procedure was followed in absence of the partic-
ular component.
128.1 (2C), 129.1 (2C), 129.3, 129.7 (2C), 132.1 (2C), 145.3; HRMS
calcd for C16H14Se (Mþ): 286.0261, found: 286.0260.
4.2.4. ((3-Fluorophenyl)ethynyl)(phenyl)selane (Table 2, entry 8).
Yield 89%, yellow viscous liquid, IR (neat): 3061, 2966, 2885, 2163,
This procedure was followed for all the reactions listed in Table 3.
Only one of these products is known compound (Table 3, entry 2) and
was identified by comparison of its spectra with those reported ear-
lier.15 The products, which were not reported earlier, were charac-
terized by their spectroscopic data (IR, 1H NMR, 13C NMR and HRMS).
These data are provided below in order of their entries in Table 3.
1684, 1568, 1566, 1498 cmꢁ1; 1H NMR (CDCl3, 500 MHz)
d
7.03e7.10
(m,1H), 7.19e7.21 (m,1H), 7.26e7.37 (m, 5H), 7.60 (d, J¼8.0 Hz, 2H);
13C NMR (CDCl3, 125 MHz)
d
71.2, 101.7 (d, J¼2.5 Hz), 116.1 (d,
J¼20.0 Hz), 118.5 (d, J¼22.5 Hz), 125.1 (d, J¼10 Hz), 127.5 (d,
J¼20 Hz), 128.70, 129.4 (2C), 129.8 (2C), 130.1, 162.50 (d, J¼243 Hz);
Anal. Calcd for C14H9FSe: C, 61.11; H, 3.30; found: C, 60.98; H, 3.32%.
4.3.1. Oct-1-yn-1-yl(phenyl)tellane (Table 3, entry 1). Yield 75%,
yellow viscous liquid, IR (neat): 3031, 3024, 2918, 2166, 1898, 1546,
4.2.5. ((6-Methoxynaphthalen-2-yl)ethynyl)(phenyl)selane (Table 2,
1413, 1236 cmꢁ1; 1H NMR (CDCl3, 500 MHz)
d
0.91 (t, J¼7.0 Hz, 3H),
entry 14). Yield 81%, pale yellow solid, mp 96 ꢀC, IR (KBr): 3059,
1.29e1.34 (m, 4H), 1.42e1.45 (m, 2H), 1.55e1.60 (m, 2H), 2.58 (t,
J¼7.0 Hz, 2H), 7.25e7.27 (m, 3H), 7.67e7.68 (m, 2H); 13C NMR
2958, 2931, 2837, 2152, 1624, 1597, 1475, 1228 cmꢁ1 1H NMR
;
(CDCl3, 500 MHz)
d
3.93 (s, 3H), 7.12 (d, J¼2.5 Hz, 1H), 7.17e7.19
(CDCl3, 125 MHz) d 14.2, 21.36, 22.7, 28.6, 29.0, 31.4, 34.9, 113.3,
(m, 1H), 7.29 (d, J¼7.0 Hz, 1H), 7.36 (t, J¼7.5 Hz, 2H), 7.52e7.54
116.3, 127.7, 129.69 (2C), 134.8 (2C); Anal. Calcd for C14H18Te: C,
53.57; H; 5.78, found: C, 52.98; H, 5.81.
(m, 1H), 7.64 (d, J¼8.0 Hz, 2H), 7.70 (t, J¼8.5 Hz, 2H), 7.97 (s, 1H);
13C NMR (CDCl3, 125 MHz)
d 55.4, 68.7, 103.7, 106.0, 118.2, 119.6,
127.0, 128.5, 129.1, 129.2 (2C), 129.3, 129.5, 129.7, 132.0 (2C), 134.5,
158.6; HRMS calcd for C19H14OSe (MþþH): 339.0288, found:
339.0285.
4.3.2. Phenyl(o-tolylethynyl)tellane (Table 3, entry 3). Yield 78%,
yellow liquid, IR (neat): 3053, 2943, 2918, 2135, 1948, 1574, 1474,
1435, 1377, 1223, 1109 cmꢁ1 1H NMR (CDCl3, 500 MHz)
; d 2.48 (s,
3H), 7.15e7.17 (m, 1H), 7.22 (d, J¼6.5 Hz, 2H), 7.26e7.29 (m, 3H),
4.2.6. 2-((Phenylselanyl)ethynyl)thiophene (Table 2, entry 15). Yield
7.44 (d, J¼7.5 Hz, 1H), 7.76 (t, J¼6.5 Hz, 2H); 13C NMR (CDCl3,
91%, yellow viscous liquid, IR (neat): 3105, 3057, 2920, 2850,
125 MHz) d 20.9, 50.8, 113.6, 125.6, 128.0, 128.7, 129.5, 129.9 (2C),
132.35, 135.1 (2C), 140.8; Anal. Calcd for C15H12Te: C, 56.33; H, 3.78;
found: C, 55.12; H, 4.01.
2154, 1674, 1575, 1475, 1356 cmꢁ1
;
1H NMR (CDCl3, 500 MHz)
d
7.15 (t, J¼5.0 Hz, 1H), 7.23e7.26 (m, 3H), 7.29e7.31 (m, 2H), 7.51
(t, J¼4.0 Hz, 1H), 7.55e7.60 (m, 1H); 13C NMR (CDCl3, 125 MHz)
d
68.9, 97.9, 122.4, 125.4, 127.2, 129.2 (2C), 129.4 (2C), 129.6, 129.9,
4.3.3. ((4-Ethylphenyl)ethynyl)(phenyl)tellane (Table 3, entry 4).
133.8; HRMS calcd for C12H8SSe (MþþH): 264.9590, found:
Yield 81%, pale yellow liquid, IR (neat): 3078, 2940,1739, 1597, 1518,
264.9609.
1344, 1228, 1109, 1028 cmꢁ1 1H NMR (CDCl3, 500 MHz)
; d 1.24 (t,
J¼7.5 Hz, 3H), 2.26e2.70 (m, 2H), 7.17 (d, J¼8.0 Hz, 2H), 7.26e7.30
4.2.7. ([1,10-Biphenyl]-4-ylethynyl)(phenyl)selane (Table 2, entry
16). Yield 89%, yellow solid, mp 98 ꢀC, IR (KBr): 3325, 3057, 2924,
2158, 1575, 1475, 1437, 1066, 1006 cmꢁ1; 1H NMR (CDCl3, 500 MHz)
(m, 3H), 7.41 (d, J¼8.5 Hz, 2H), 7.74e7.76 (m, 2H); 13C NMR (CDCl3,
125 MHz) d 15.5, 28.9, 46.3, 113.5, 114.7, 120.8, 128.0 (2C), 130.0 (2C),
132.28 (3C), 135.1 (2C), 145.3; Anal. Calcd for C16H14Te: C, 57.56; H,
4.23; found: C, 58.01; H, 4.31.
d
7.26e7.30 (m, 1H), 7.34e7.39 (m, 3H), 7.46 (t, J¼7.5 Hz, 2H),
7.59e7.63 (m, 8H); 13C NMR (CDCl3, 125 MHz)
d
70.1, 103.0, 122.2,
127.1 (2C), 127.3, 127.8 (2C), 129.0 (2C), 129.1, 129.2 (2C), 129.7 (2C),
132.3 (2C), 140.4, 141.4; Anal. Calcd for C20H14Se: C, 72.07; H, 4.23;
found: C, 71.90; H, 4.25%.
4.3.4. ((4-Methoxyphenyl)ethynyl)(phenyl)tellane (Table 3, entry
5). Yield 83%, pale yellow liquid, IR (neat): 3285, 3051, 2958, 2835,
2137, 1603, 1572, 1506, 1292, 1249, 1171, 1032 cmꢁ1; 1H NMR (CDCl3,

S. Ahammed et al. / Tetrahedron 68 (2012) 10542e10549
10549
500 MHz)
d
3.71 (s, 3H), 6.73e6.77 (m, 3H), 7.15e7.18 (m, 2H),
(2C), 129.9 (2C), 132.5 (2C), 135.3 (2C), 140.4, 141.5; Anal. Calcd for
C20H14Te: C, 62.90; H, 3.69, found: C, 61.94; H, 3.21.
7.32e7.35 (m, 2H), 7.63e7.65 (m, 2H); 13C NMR (CDCl3, 125 MHz)
d
45.3, 55.4, 113.6, 114.0 (2C), 114.4, 115.7, 127.9, 129.8 (2C), 133.8
(2C), 135.1 (2C), 160.1; HRMS calcd for C15H12OTe (MþþNa):
Acknowledgements
360.9848, found: 360.9817.
We are pleased to acknowledge financial support from CSIR,
New Delhi [Grant no. 01(2365)/10/EMR-II] for this investigation.
S.A., S.B. and D.K. also thank CSIR for their fellowships.
4.3.5. ((4-Bromophenyl)ethynyl)(phenyl)tellane (Table 3, entry 6).
Yield 85%, yellow viscous liquid, IR (neat): 3070, 3053, 2162, 1576,
1475, 1437, 1390, 1066, 1008, 823 cmꢁ1; 1H NMR (CDCl3, 500 MHz)
d
7.16e7.25 (m, 5H), 7.38 (d, J¼8.5 Hz, 2H), 7.66 (t, J¼6.0 Hz, 2H); 13
C
Supplementary data
NMR (CDCl3, 125 MHz) d 49.2, 113.0, 113.2, 122.5, 123.0, 128.3, 130.0
(2C), 139.7 (2C), 133.4 (2C), 135.6 (2C); Anal. Calcd for C14H9BrTe: C,
43.71; H, 2.36, found: C, 43.24; H, 2.40.
Supplementary data (1H NMR and 13C NMR spectra of all
products listed in Table 2 and Table 3). Supplementary data
related to this article can be found at http://dx.doi.org/10.1016/
j.tet.2012.08.046.
4.3.6. ((4-Chlorophenyl)ethynyl)(phenyl)tellane (Table 3, entry 7).
Yield 87%, pale yellow viscous liquid, IR (neat): 3049, 2965, 2137,
1572, 1506, 1474, 1435, 1016 cmꢁ1 1H NMR (CDCl3, 500 MHz)
;
References and notes
d
7.19e7.24 (m, 5H), 7.31 (d, J¼9.0 Hz, 2H), 7.66e7.68 (m, 2H), 13
C
1. Devillanova, F. A. Handbook of Chalcogen Chemistry: New Perspectives in S, Se and
Te; Royal Society of Chemistry: Cambridge, UK, 2006.
2. Comasseto, J. V.; Menezes, P. H.; Stefani, H. A.; Zeni, G.; Braga, A. L. Tetrahedron
1996, 52, 9687e9702.
3. Petrov, M.; Radchenko, S. I.; Kupin, V. S.; Petrov, A. A. J. Org. Chem. (USSR) 1973,
9, 683e685.
4. Yang, D. Y.; Huang, X. J. J. Organomet. Chem. 1997, 543, 165e169.
5. Tingolli, M.; Tieco, M.; Testaferri, L.; Temperini, A. Tetrahedron 1995, 51,
4691e4700.
6. Magriotis, P. A.; Brown, J. T.; Scolt, M. E. Tetrahedron Lett. 1991, 32, 5047e5050.
7. Zhu, L. S.; Huang, Z. Z.; Huang, X. J. J. Chem. Res., Synop. 1996, 112e114.
8. Ma, Y.; Qian, C. Tetrahedron Lett. 2000, 41, 945e947.
9. Xu, W. M.; Tang, E.; Huang, X. Tetrahedron 2005, 61, 501e506.
10. Leonard, K. A.; Nelen, M. L.; Simard, T. P.; Davies, S. R.; Gollnick, S. O.; Oseroff, A. R.;
Gibson, S. L.; Hilf, R.; Chen, L. B.; Detty, M. R. J. Med. Chem. 1999, 42, 3953e3964.
11. Lang, H.; Keller, H.; Imhof, W.; Martin, S. Chem. Ber. 1990, 123, 417e422.
12. Bieber, L. W.; da Silva, M. F.; Menezes, P. H. Tetrahedron Lett. 2004, 45, 2735e2737.
13. Rampon, D. S.; Giovenardi, R.; Silva, T. L.; Rambo, R. S.; Merlo, A. A.; Schneider,
P. H. Eur. J. Org. Chem. 2011, 7066e7070.
NMR (CDCl3, 125 MHz)
d 49.0, 113.0, 113.1, 122.0, 128.3, 128.8 (2C),
130.0 (2C), 133.25 (2C), 134.8, 135.5 (2C); HRMS calcd for C14H9ClTe
(MþþH): 342.9533, found: 342.9531.
4.3.7. ((6-Methoxynaphthalen-2-yl)ethynyl)(phenyl)tellane (Table 3,
entry 8). Yield 76%, pale yellow solid, mp 98 ꢀC IR (KBr): 3085,
3023, 2161, 1584, 1473, 1357, 1218 cmꢁ1; 1H NMR (CDCl3, 500 MHz)
d
3.80 (s, 3H), 6.99 (s, 1H), 7.05 (d, J¼8.5 Hz, 1H), 7.18 (d, J¼4.5 Hz,
3H), 7.38 (d, J¼8.5 Hz, 1H), 7.55e7.58 (m, 2H), 7.67 (t, J¼6.5 Hz, 2H),
7.81 (s, 1H); 13C NMR (CDCl3, 125 MHz)
46.8, 55.4, 65.8, 106.0,
d
113.4, 115.0, 118.4, 119.5, 127.0, 128.0, 128.4, 129.3, 129.5, 130.0,
132.0, 132.2, 134.5, 135.2, 158.6; Anal. Calcd for C19H14OTe: C, 59.13;
H, 3.66; found: C, 58.37; H, 3.58.
4.3.8. 2-((Phenyltellanyl)ethynyl)thiophene (Table 3, entry 9). Yield
14. Braga, A. L.; Reckziegel, A.; Menezes, P. H.; Stefani, H. A. Tetrahedron Lett. 1993,
34, 393e394.
15. Sharma, A.; Schwab, R. S.; Braga, A. L.; Barcellos, T.; Paixao, M. W. Tetrahedron
82%, pale yellow liquid, IR (neat): 3103, 3051, 2137, 1572, 1473, 1435,
1354, 1016 cmꢁ1; 1H NMR (CDCl3, 500 MHz)
d
7.17 (d, J¼5.0 Hz, 1H),
Lett. 2008, 49, 5172e5174.
7.26e7.30 (m, 4H), 7.51 (d, J¼2.5 Hz, 1H), 7.75e7.76 (m, 2H); 13C
16. Das, J. P.; Roy, U. K.; Roy, S. Organometallics 2005, 24, 6136e6140.
17. Bhadra, S.; Ranu, B. C. Adv. Synth. Catal. 2009, 351, 2369e2978.
18. Ranu, B. C.; Mandal, T.; Samanta, S. Org. Lett. 2003, 5, 1439e1441.
19. Handbook for X-ray Photoelectron Spectroscopy, Chastain, J.; Roger, Jr. C.K. Eds.,
Physical Electronics, Eden Prairie, MN.
NMR (CDCl3, 125 MHz)
d 47.1, 109.0, 113.2, 122.7, 125.3, 128.1, 129.9
(2C), 130.1, 130.3, 135.3 (2C); Anal. Calcd for C12H8STe: C, 46.22; H,
2.59, found: C, 45.68; H, 2.12.
20. Choudary, B. M.; Sridhar, C.; Kantam, M. L.; Venkanna, G. T.; Sreedhar, B. J. J. Am.
4.3.9. ([1,10-Biphenyl]-4-ylethynyl)(phenyl)tellane (Table 3, entry 10).
Chem. Soc. 2005, 127, 9948e9949.
21. Bhadra, S.; Saha, A.; Ranu, B. C. J. Org. Chem. 2010, 75, 4864e4867.
22. Mu, Z.; Shu, L.; Fuchs, H.; Mayor, M.; Chi, L. J. Am. Chem. Soc. 2008, 130,
10840e10841.
Yield 83%, pale yellow solid, mp 101 ꢀC, IR (KBr): 3286, 3053, 2924,
1599, 1572, 1479, 1433, 1261 cmꢁ1 1H NMR (CDCl3, 500 MHz)
;
23. Braga, A. L.; Silviera, C. C.; Reckziegel, A.; Menezes, P. H. Tetrahedron Lett. 1993,
34, 8041e8042.
24. Mitamura, T.; Ogawa, A. Tetrahedron Lett. 2010, 51, 3538e3541.
25. Huang, X.; Sun, A. J. Org. Chem. 2000, 65, 6561e6565.
d
7.26e7.31 (m, 3H), 7.37 (t, J¼7.0 Hz, 1H), 7.44e7.48 (m, 2H),
7.54e7.63 (m, 6H), 7.76 (t, J¼7.5 Hz, 2H); 13C NMR (CDCl3, 125 MHz)
d
48.2, 113.3, 114.3, 122.4, 127.2 (2C), 127.3 (2C), 127.8, 128.1, 129.1