Short and efficient preparation of alkynyl selenides, sulfides and tellurides from terminal alkynes

Article abstract of DOI:10.1016/j.tetlet.2004.02.042

Diphenyl diselenide reacts with terminal alkynes at room temperature in DMSO in the presence of catalytic amounts of copper iodide to give good to excellent yields of alkynyl phenyl selenides. The reaction occurs under neutral conditions and the solvent a

Full text of DOI:10.1016/j.tetlet.2004.02.042

Tetrahedron
Letters
Tetrahedron Letters 45 (2004) 2735–2737
Short and efficient preparation of alkynyl selenides, sulfides and
tellurides from terminal alkynes
Lothar W. Bieber,* Margarete F. da Silva and Paulo H. Menezes
Departamento de Quꢀımica Fundamental, Universidade Federal de Pernambuco, Recife PE 50670-901, Brazil
Received 16 January 2004; revised 6 February 2004; accepted 10 February 2004
Abstract—Diphenyl diselenide reacts with terminal alkynes at room temperature in DMSO in the presence of catalytic amounts of
copper iodide to give good to excellent yields of alkynyl phenyl selenides. The reaction occurs under neutral conditions and the
solvent acts as the oxidant. Diphenyl disulfide and ditelluride undergo the analogous reaction, but require the presence of a weak
inorganic base.
Ó 2004 Published by Elsevier Ltd.
Alkynyl chalcogenides are useful intermediates for the
synthesis of several compounds and can be used as
versatile building blocks for a variety of chemical pur-
poses.1
species, which has to be performed under strictly
anhydrous conditions, limiting thus the scope to base
resistant substrates. Although methodologies based on
the use of copper were also described,18 these procedures
suffer disadvantages in terms of yields, or unattractive
reaction conditions. Indeed, the tedious work up pro-
cedure under basic conditions necessary to eliminate
large amounts of cuprous and cupric salts affected purity
and yield of the isolated products, especially in the case
of functionalized alkynes. Similar procedures using
diphenyl disulfide and ditelluride gave even less satis-
factory results. An alternative preparation has reported
comparable yields using iodobenzene diacetate, a rather
exotic and expensive oxidant.19
Many methods based on selenium have been developed
into standard procedures in organic chemistry. Alkynyl
selenides, for example, can be transformed into the
corresponding functionalized vinylic selenides by
hydroamination,2 hydrohalogenation,3 hydrosulfona-
tion,4 hydrostannylation,5 hydrozirconation6 and hydro-
boration.7 Additionally, these compounds can be used
in cycloaddition reactions,8 addition of nucleophiles
such as butyl cyanocuprate9 and in the formation of
selenonium salts.10 Likewise, alkynyl sulfides can be
used in cycloadditon,11 and cross-coupling reactions,12
as well as in the preparation of self-assembled mono-
layers in the production of composite materials.13
Although there are no specific mechanistic studies, all
such reactions suggest alkynyl radicals as intermediates.
Having in mind the known dimerization of copper
acetylides on thermolysis or in the presence of oxygen
and the well established reactivity of diphenyl diselenide
as a radical scavenger, we envisaged the possibility that
alkynes might react with diphenyl diselenide in the
presence of base and a catalytic amount of copper (I),
which should be recycled by oxygen or another oxidant
according to Scheme 1.
During the last few years, alkynyl tellurides have been
studied little. Although organotellurium compounds
have attracted considerable interest as reagents and
intermediates in organic synthesis,14 as monomers for
conducting materials,15 as MOCVD precursors to metal
telluride films16 and in medical applications.17
Most of the methodologies to synthesize alkynyl chalco-
genides are based on the generation of organometallic
CuI (cat.)
R
SePh
R
+ 0.5 (PhSe)2
DMSO
25oC
Keywords: Alkynyl selenides; Alkynyl sulfides; Alkynyl tellurides.
* Corresponding author. Tel.: +55-81-3271-8440; fax: +55-81-3271-
8442; e-mail: bieberlothar@hotmail.com
Scheme 1.
0040-4039/$ - see front matter Ó 2004 Published by Elsevier Ltd.
doi:10.1016/j.tetlet.2004.02.042

2736
L. W. Bieber et al. / Tetrahedron Letters 45 (2004) 2735–2737
First attempts using propargyl alcohol carried out in
commercial, undried acetonitrile or DMF in an air
atmosphere showed no reaction at all in the presence of
copper iodide (0.05 equiv) and potassium carbonate
(1.0 equiv). However, when DMSO was chosen as the
solvent a smooth and clean reaction took place in 4 h at
room temperature yielding 56% of the desired selenide
(Table 1, entry 1). In the absence of base, the reaction
rate was slower, but the yield raised to 69% after 20 h
(entry 2). CuI proved to be the best catalyst, as reactions
in the presence of CuCl, CuBr, CuCN and CuCl2 gave
only trace amounts of product (entries 3–6). A control
experiment in the absence of any copper catalyst showed
no reaction at all. On the other hand, the CuI catalyzed
reaction worked equally well in carefully degassed
solution under Ar atmosphere; this surprising result
together with the lack of reactivity in other solvents
suggests that DMSO acts not only as the solvent, but
also as the oxidant.20
[CuI]
R
YPh
+ 0.5 PhYYPh
Y =S, Te
R
DMSO, K2CO3
30oC
Scheme 2.
Table 3. Alkynyl sulfides and tellurides prepared according to Scheme
2
Entry
R
Y
Time (h)
Yield (%)
1
CH2OHa
S
20
20
20
20
72
20
20
20
20
72
20
20
72
72
20
20
20
20
50
80
94
99
96
85
80
90
82
30b
69
50
83
92
80
30
65
65
2
CH2CH2OHa
C(CH3)2OH
C6H5
S
3
S
4
S
a
5
n-C4H9
S
6
CO2C2H5
TMSa
S
7
S
8
CH2OTHP
CH2OTBDMS
CH2OHa
S
9
S
10
11
12
13
14
15
16
17
18
Te
Te
Te
Te
Te
Te
Te
Te
Te
CH2CH2OHa
C(CH3)2OHc
C6H5
When the optimized procedure of entry 2 was used with
other alkynols, aliphatic and aromatic alkynes and ethyl
propiolate, complete reaction and nearly quantitative
yields of selenides were obtained (Table 2).21 In all cases
chromatographic purification was unnecessary and pure
products were obtained after aqueous workup, extrac-
tion and crystallization or short path distillation.
a
n-C4H9
CO2C2H5
TMSa
c
CH2OTHP
CH2OTBDMS
a An excess of 0.5 mmol of alkyne was used.
b Determined by 1H NMR in the crude extract.
c KHCO3 was used as a base.
Encouraged by these results we examined analogous
reactions with diphenyl disulfide and ditelluride (Scheme
2).
In the absence of base, no reaction at all was observed
with both reagents even after several days at room
temperature. However, 1 equiv of solid potassium
carbonate was sufficient to produce alkynyl phenyl
sulfides in excellent yields (Table 3, entries 1–9).
The only exception was propargyl alcohol, which once
more gave the lowest yield (Table 3, entry 2). The same
alcohol gave even less satisfactory results with diphenyl
ditelluride; large amounts of disproportionation and
degradation products were formed under standard
conditions (Table 3, entry 10). The protected derivatives,
however, gave the desired products in good yields (Table
3, entries 8, 9, 17 and 18). Other alkynols and unfunc-
tionalized alkynes reacted better and even ethyl propi-
olate gave a clean reaction when the weaker base
KHCO3 was used (Table 3, entries 11–16).
Table 1. Influence of catalyst on the formation of selenides
conditions
+ 0.5 (PhSe)2
SePh
HO
HO
Entry
Conditions
Yield (%)
1
2
3
4
5
6
DMSO, CuI, K2CO3, 30 °C, 20 h
DMSO, CuI, 30 °C, 20 h
DMSO, CuCl, 30 °C, 20 h
DMSO, CuBr, 30 °C, 20 h
DMSO, CuCN, 30 °C, 20 h
DMSO, CuCl2, 30 °C, 20 h
56
69
2
2
3
In summary, we reported here a general, mild and effi-
cient synthesis of alkynyl phenyl chalcogenides. Its
major advantages in comparison with known methods
are: atom economy by the use of both chalcogen atoms
of the starting material, catalytic amounts of copper
iodide, undried and nontoxic solvent, no inert atmo-
sphere, simple reaction and work up procedures.
2
Table 2. Alkynyl selenides prepared according to Scheme 1
Entry
R
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
CH2OHa
20
72
20
20
72
20
20
20
20
69
71
95
97
90
96
80
85
90
CH2CH2OHa
C(CH3)2OH
C6H5
a
n-C4H9
CO2C2H5
TMSa
Acknowledgements
CH2OTHP
CH2OTBDMS
We gratefully acknowledge the support from CNPq and
CNPq/PROFIX (54045/01-4).
a An excess of 0.5 mmol of alkyne was used.

L. W. Bieber et al. / Tetrahedron Letters 45 (2004) 2735–2737
2737
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21. General experimental procedure: A mixture of 0.25 mmol
of the alkyne, 0.125 mmol of diphenyl dichalcogenide,
0.01 mmol of CuI and 0.5 mmol of base (where indicated)
in 1.0 ml of commercial, undried DMSO was stirred at
room temperature for the indicated time. After aqueous
acidic work up and extraction with ether or dichloro-
methane, the crude products were purified by crystalliza-
tion or distillation.