A General and highly efficient protocol for the synthesis of chalcogenoacetylenes by copper(I)-terpyridine catalyst

Article abstract of DOI:10.1055/s-0033-1341277

A highly efficient copper-catalyzed C_sp-X (X = S, Se, Te) bond-forming reaction of terminal alkynes and diorganyl dichalcogenides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 4′-(4-meth

Full text of DOI:10.1055/s-0033-1341277

LETTER
▌1385
lAetteGr eneral and Highly Efficient Protocol for the Synthesis of Chalcogeno-
acetylenes by Copper(I)-Terpyridine Catalyst
Synthesis of Chalcogenoacetylenes
Barahman Movassagh,* Ali Yousefi, Badri Zaman Momeni,* Sepideh Heydari
Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran
E-mail: bmovass1178@yahoo.com; E-mail: momeni@kntu.ac.ir
Received: 04.02.2014; Accepted after revision: 31.03.2014
alkynyl bromides with a nucleophilic source of seleni-
um;16a (iii) elimination of nitrogen by cleavage of seleno-
diazoles in the presence of an alkylating agent;18 (iv)
selenodecarboxylation of either arylpropiolic or cinnamic
Abstract: A highly efficient copper-catalyzed Csp–X (X = S, Se,
Te) bond-forming reaction of terminal alkynes and diorganyl di-
chalcogenides has been developed. This transformation was real-
ized through the use of copper(I) iodide as a catalyst, 4′-(4-
methoxyphenyl)-2,2′:6′,2′′-terpyridine as a ligand, and K3PO4 as a acid derivatives with diorganyl diselenide promoted by
base. A variety of the functionalized substrates were found to react
under these reaction conditions to provide products in good to ex-
cellent yields.
hypervalent iodine species such as iodosylbenzene (IB)
and iodosobenzene diacetate (IBDA);19 and (v) the reac-
tion of metal alkynylide with elemental selenium,20 or an
Key words: alkynyl chalcogenides, diorganyl dichalcogenides, ter-
minal alkynes, terpyridines, copper-catalyzed reaction
appropriate electrophilic selenium agent, such as seleno-
cyanates,21 arylselenium halides,22 or diaryl diselenides.23
However, the commonly used method for the synthesis of
alkynyl selenides is based on a copper-assisted cross-cou-
Transition-metal catalysis of carbon–heteroatom bond
formation are of great demand in general organic synthe-
sis as well as the pharmaceutical industry and material sci-
ence application.1,2 In the last two decades, there has been
a resurgence in interest in developing mild synthetic
methods based on the copper-based catalysts as an alter-
native to other metal catalysts for the formation of Csp–X
(X = S, Se, Te) bonds.
pling reaction of terminal alkynes with a suitable source
of electron-deficient selenium.16d–h,24 Although synthetic
routes based on organometallic species for the preparation
of acetylenic selenides are widely used, these procedures
suffer from several disadvantages such as using stoichio-
metric amount of toxic metal salts,20 high tempera-
tures,16b,25 and performing anhydrous conditions.26
Besides, similar reaction conditions applying for prepara-
tion of alkynyl sulfides and tellurides exhibit less accept-
able results. Therefore, development of a new general
approach for the synthesis of these types of organochalco-
genes, especially for the efficient synthesis of alkynyl sul-
fides and tellurides, remains highly desirable. Because of
the importance and current interest in Csp–X coupling re-
actions, we decided to investigate the copper-catalyzed
C–X bond formation between terminal alkynes and di-
chalcogenides (X = S, Se, Te) via the utilization of air-sta-
ble copper salt and a 4′-substituted terpyridine ligand.
Due to their fundamental roles in many organic transfor-
mations, many different classes of organochalcogenes
have been prepared and studied to date.3 Also, these class-
es of compounds are widely found in many biologically
active and natural molecules like antioxidant, antitumor,
antimicrobial, and antiviral.4 In addition, organochalco-
genes have been extensively used for technological pur-
poses which is based on organic materials such as organic
semiconductors and liquid crystals.5 Among organochal-
cogenes, alkynyl chalcogenides can be employed as po-
tent building blocks for a variety of chemical purposes.6
For example, alkynyl selenides can be used in the synthe-
sis of substituted olefins by hydroamination,7 hydrohalo-
The tridentate 2,2′:6′,2′′-terpyridines (tpys) have been of
great interest over the last few years, mostly because of
their ability to chelate transition metals.27 Furthermore,
they are widely used in various research fields, such as
medicinal chemistry,28 photochemistry,29 organometal-
lics,30 and nanoscience.31 Herein, we report a simple, in-
expensive, and efficient catalytic system for the synthesis
of alkynyl chalcogenides by using CuI and 4′-(4-me-
thoxyphenyl)-2,2′:6′,2′′-terpyridine (Mtpy)32 under mild
reaction conditions.
gentation,8
hydroboration,9
hydrosulfonation,10
hydrostannylation,11 and hydrozirconation.12 Further-
more, they are useful precursors in cycloaddition reac-
tions, preparation of selenium salts,13 and in the formation
of selenol esters which are mild acyl-transferring agents.14
Also, alkynyl sulfides can be utilized in cycloaddition and
cross-coupling reactions.15 However, there are limited re-
ports of alkynyl tellurides’ synthesis in the literature.16a–f
Phenylacetylene (1a) and diphenyl diselenide (2a) were
used as substrates for the initial optimization of the reac-
tion at 50 °C. The influences of the reaction parameters
are summarized in Table 1. As expected, the model reac-
tion did not occur in the absence of catalyst (Table 1, entry
1) while only a 64% yield was obtained after 18 hours in
the absence of the ligand in DMSO (Table 1, entry 2).
Alkynyl selenides are usually prepared by one of the five
methods: (i) Coupling of terminal alkynes with diorganyl
diselenides in the presence of a base;17 (ii) the reaction of
SYNLETT 2014, 25, 1385–1390
Advanced online publication: 12.05.2014
0
9
3
6
-
5
2
1
4
1
4
3
7
-
2
0
9
6
DOI: 10.1055/s-0033-1341277; Art ID: st-2014-d0094-l
© Georg Thieme Verlag Stuttgart · New York

1386
B. Movassagh et al.
LETTER
Among the screened copper(I) salts, copper(I) iodide re- them, 1 mol% of each were found to be the best (Table 1,
sulted in the best performance (Table 1, entries 7–11).
entry 7). No significant change in the yield value of prod-
uct was observed (96% isolated yield) when the reaction
was conducted under inert (N2) atmosphere. Lowering the
temperature from 50 °C to 40 °C had a substantial reduc-
tion of the product yield (Table 1, entry 7). Therefore, the
optimal reaction conditions were: diphenyl diselenide (1
equiv), phenylacetylene (2.0 equiv), CuI (1 mol%), Mtpy
ligand (1 mol%), and K3PO4 (2 equiv) stirred in DMSO
(4 mL) at 50 °C for five minutes in air.33
Among the tested organic and inorganic bases, K3PO4 was
found to be the most suitable base (Table 1, entries 12–
17). For the solvent, DMSO resulted in the highest yield
among the surveyed solvents (Table 1, entries 3–5). The
solventless conditions were also studied, but compared to
DMSO, it gave an inferior result (Table 1, entry 6). In ad-
dition, different copper (0.5 mol% and 1 mol%) and li-
gand (0.5 mol%, 1 mol%, and 2 mol%) concentrations
were investigated (Table 1, entries 7 and 18–20); among
Table 1 Optimization of the Reaction Conditionsa
N
CuI, Mtpy
Ph
H
+
PhSeSePh
Ph
SePh
N
MeO
Mtpy
base, solvent, 50 °C
3a
1a
2a
N
Entry
Catalyst (mol%)
Mtpy (mol%)
Base
Solvent
Time
Yield (%)b
1
2
–
1
–
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
0.5
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
Cs2CO3
K2CO3
KOH
DMSO
DMSO
DMF
24 h
18 h
n.r.
CuI (1)
CuI (1)
CuI (1)
CuI (1)
CuI (1)
CuI (1)
CuBr (1)
CuCl (1)
Cu2O (1)
CuOAc (1)
CuI (1)
CuI (1)
CuI (1)
CuI (1)
CuI (1)
CuI (1)
CuI (0.5)
CuI (1)
CuI (1)
64
3
5 min
87
4
EtOH
24 h
24 h
24 h
42
5
CHCl3
–
36
6
35
7
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
5 min
97 (75)c
12
8
5 min
9
5 min
10
10
11
12
13
14
15
16
17
18
19
20
5 min
16
5 min
25
10 min
84
10 min
93
10 min (90 min)
10 min (12 h)
10 min (12 h)
10 min (2 h)
2 h
43 (78)
10 (45)
15 (60)
31 (78)
72
DIPEAd
Et3N
DABCO
K3PO4
K3PO4
K3PO4
5 min
94
2 h
84
a Reaction conditions: diphenyl diselenide (1 mmol), phenylacetylene (2.0 mmol), base (2.0 mmol), and solvent (4 mL) at 50 °C in air.
b Isolated yield.
c Reaction was performed at 40 °C.
d N,N-Diisopropylethylamine.
Synlett 2014, 25, 1385–1390
© Georg Thieme Verlag Stuttgart · New York

LETTER
Synthesis of Chalcogenoacetylenes
1387
To determine the scope of the catalytic system, the present since the treatment of phenylacetylene with diselenides
protocol was applied in the reactions of a range of termi- containing either an electron-donating or -withdrawing
nal alkynes and diorganyl dichalcogenides (Table 2). group attached at the para position of the aromatic ring af-
First, a range of alkynyl selenides were synthesized by the forded the corresponding products in high yields (Table 2,
reaction of diorganyl diselenides with different acety- entries 2–4). Interestingly, aryl- and nonaryl-substituted
lenes. We found that this protocol was applicable to aro- alkynes gave uniform results in terms of reaction time
matic as well as aliphatic diselenides and alkynes. In (0.1–2 h) and yield (72–97%). Reaction of ethyl propio-
terms of electronic effects, the reaction was not sensitive, late proceeded at relatively higher rate compared with
Table 2 Copper-Catalyzed Synthesis of Alkynyl Chalcogenidesa
CuI (1 mol%), Mtpy (1 mol%)
R1
H
R2YYR2
R1
Y
R2
+
DMSO, K3PO4, 50 °C
2
1
3
Y = Se, S, Te
Entry
1
R1
Ph
R2
Y
Product
Time (h)
0.1
Yield (%)b
97
Ph
Se
3a
3b
Ph
Ph
SePh
Se
OMe
2
3
4
Ph
Ph
Ph
4-MeOC6H4
Se
Se
Se
0.25
0.2
90
90
92
Ph
Se
Se
Me
Cl
4-MeC6H4
4-ClC6H4
3c
Ph
Ph
3d
0.1
Se
5
Ph
PhCH2
Se
3e
1
72
Ph
SeMe
6
7
Ph
Me
Ph
Se
Se
3f
1
1
85
84
SePh
n-Bu
3g
Cl
Se
8
n-C5H11
4-ClC6H4
Se
3h
0.5
90
SePh
9
CH2OH
CO2Et
Ph
Ph
Se
Se
3i
3j
2
87
97
HO
O
10
0.5
SePh
EtO
Ph
SPh
11
12
Ph
Ph
Ph
S
S
3k
3l
3
73
56
n-C6H13
SPh
15
SPh
SPh
13
14
CH2OH
CO2Et
Ph
Ph
S
S
3m
3n
7
2
63
80
HO
O
EtO
Ph
TePh
15
16
Ph
Ph
Ph
Te
Te
3o
3p
2
2
75
87
Me
Ph
Te
TePh
4-MeC6H4
17
18
CH2OH
CO2Et
Ph
Ph
Te
Te
3q
3r
3
1
71
82
HO
O
TePh
EtO
a Reaction conditions: diorganyl dichalcogenide (1.0 mmol), alkyne (2.0 mmol), K3PO4 (2.0 mmol), CuI (1 mol%), Mtpy (1 mol%), DMSO
(4 mL) at 50 °C.
b Isolated yield.
© Georg Thieme Verlag Stuttgart · New York
Synlett 2014, 25, 1385–1390

1388
B. Movassagh et al.
LETTER
those of other aliphatic alkynes, which can be attributed to cellent yields in relatively short reaction times under mild
facile deprotonation of this terminal alkyne (Table 2, en- and aerobic conditions.
try 10).
Disulfides underwent similar reactions as diselenides, but
in most cases longer reaction times and lower yields were
observed compared to those of diselenides (Table 2, en-
tries 11–14). Then, we examined the tellurylation reaction
of various acetylenes (Table 2, entries 15–18). The reac-
tion proceeded uniformly irrespective of the nature of ter-
minal alkynes, and the corresponding products were
obtained in relatively lower yields (71–87%) and in rather
longer reaction times (1–3 h) than those of their diselenide
counterparts.
Acknowledgement
We gratefully acknowledge the funding support received for this
project by the K. N. Toosi University of Technology Research
Council. We are also thankful to Professor M. Joshaghani for his
useful comments.
Supporting Information for this article is available online
at
http://www.thieme-connect.com/products/ejournals/journal/
10.1055/s-00000083.SunogIpimrfiantoSuIpg
n
fonirtat
ori
In general, almost all chalcogenoacetylenes obtained
smoothly, in high yields, and in short reaction times. Sev-
eral functionalities, such as OH, CO2Et, OMe, and Cl are
well accepted in this reaction.
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Scheme 1 Plausible reaction pathway
In summary, we have introduced a general and highly ef-
ficient copper-catalyzed procedure for the synthesis of al-
kynyl chalcogenides from terminal acetylenes and
diorganyl dichalcogenides using K3PO4 as base and terpy-
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compatible with these reaction conditions. This new pro-
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Synlett 2014, 25, 1385–1390
© Georg Thieme Verlag Stuttgart · New York

LETTER
Synthesis of Chalcogenoacetylenes
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To the suspension of K3PO4 (2.0 mmol) in dry DMSO
(4 mL) diorganyl dichalcogenide (1.0 mmol) and terminal
acetylene (2.0 mmol) were added, and the mixture was
stirred at 50 °C. Then, CuI (1.0 mol%) and Mtpy (1.0 mol%)
were added to the above mixture, and the reaction mixture
was stirred at that temperature under aerobic conditions. The
progress of the reaction was monitored by TLC. When the
reaction was complete, the mixture was poured into H2O (15
mL) and extracted with EtOAc (2 × 15 mL). The combined
organic layers were dried over MgSO4, filtered, and
concentrated in vacuo to give the crude product which was
further purified by preparative TLC (silica gel, n-hexane–
EtOAc = 9:1). The identity and purity of the products were
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Phenyl(2-phenylethynyl)selane (3a)
Yellow oil. IR (neat): ν = 2200 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 7.61 (d, J = 9 Hz, 2 H), 7.50–7.51 (m, 2 H),
7.32–7.37 (m, 6 H). 13C NMR (75 MHz, CDCl3): δ = 131.7,
129.5, 129.0, 128.9, 128.6, 128.3, 127.1, 123.2, 102.9, 69.2.
(4-Methoxyphenyl)(2-phenylethynyl)selane (3b)
Yellow oil. IR (neat): ν = 2208 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 7.58 (d, J = 8.8 Hz, 2 H), 7.34–7.48 (m, 5 H),
6.88 (d, J = 8.8 Hz, 2 H), 3.82 (s, 3 H). 13C NMR (75 MHz,
CDCl3): δ = 159.7, 133.7, 131.9, 128.6, 128.1, 121.1, 120.2,
115.0, 101.1, 70.4, 55.3.
(17) Movassagh, B.; Navidi, M. Chin. Chem. Lett. 2012, 23,
1035.
(18) Abramov, M. A.; Dehaen, W.; D’hooge, B.; Petrov, M. L.;
Smeets, S.; Toppet, S.; Voets, M. Tetrahedron 2000, 56,
3933.
Benzyl(2-phenylethynyl)selane (3e)
Yellow oil. IR (neat): ν = 2156 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 7.22–7.42 (m, 10 H), 3.74 (s, 2 H). 13C NMR (75
MHz, CDCl3): δ = 139.2, 137.5, 132.4, 131.4, 129.1, 128.2,
126.7, 123.5, 101.3, 68.1, 32.7.
(19) Das, J. P.; Roy, U. K.; Roy, S. Organometallics 2005, 24,
6136.
(20) Takimiya, K.; Jigami, T.; Kawashima, M.; Kodani, M.; Aso,
Y.; Otsubo, T. J. Org. Chem. 2002, 67, 4218.
(21) Werz, B. D.; Gleiter, R.; Rominger, F. J. Org. Chem. 2002,
67, 4290.
Methyl(2-phenylethynyl)selane (3f)
Orange oil. IR (neat): ν = 2201 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 7.96–7.99 (m, 2 H), 7.86–7.89 (m, 3 H), 2.28 (s,
3 H). 13C NMR (75 MHz, CDCl3): δ = 135.2, 129.99, 129.97,
125.1, 103.3, 73.2, 8.7.
(Hex-1-ynyl)(phenyl)selane (3g)
(22) (a) Back, T. G.; Bethell, R. J.; Parvez, M.; Wehrli, D. J. Org.
Chem. 1998, 63, 7908. (b) Rampon, D. S.; Giovenardi, R.;
Silva, T. L.; Rambo, R. S.; Merlo, A. A.; Schneider, P. H.
Eur. J. Org. Chem. 2011, 7066.
(23) Cook, D. J.; Hill, A. F.; Wilson, D. J. J. Chem. Soc., Dalton
Trans. 1998, 1171.
Yellow oil. IR (neat): ν = 2197 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 7.52 (d, J = 8.2 Hz, 2 H), 7.21–7.31 (m, 3 H),
2.47 (t, J = 6.9 Hz, 2 H), 1.61 (quin, J = 6.8 Hz, 2 H), 1.47
(sext, J = 7.2 Hz, 2 H), 0.94 (t, J = 7.2 Hz, 3 H). 13C NMR
(75 MHz, CDCl3): δ = 133.0, 129.4, 128.6, 126.7, 104.7,
57.3, 30.8, 21.98, 20.3, 14.1, 13.6.
(24) Mohammadi, E.; Movassagh, B. Tetrahedron Lett. 2014, 55,
1613.
(25) Lara, R. G.; Rosa, P. C.; Soares, L. K.; Silva, M. S.; Jacob,
R. G.; Perin, G. Tetrahedron 2012, 68, 10414.
3-(Phenylselanyl)prop-2-yn-1-ol (3i)
Yellow oil. IR (neat): ν = 3339, 3059 cm–1. 1H NMR (300
MHz, CDCl3): δ = 7.51–7.63 (m, 2 H), 7.26–7.37 (m, 3 H),
4.15 (s, 2 H), 1.96 (br s, 1 H). 13C NMR (75 MHz, CDCl3):
δ = 132.3, 130.3, 129.4, 127.6, 101.5, 67.5, 64.9.
© Georg Thieme Verlag Stuttgart · New York
Synlett 2014, 25, 1385–1390

1390
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LETTER
Phenyl(2-phenylethynyl)sulfane (3k)
CDCl3): δ = 7.30–7.38 (m, 3 H), 7.21–7.27 (m, 2 H), 4.55 (q,
J = 6.9 Hz, 2 H), 1.54 (t, J = 6.9 Hz, 3 H). 13C NMR (75
MHz, CDCl3): δ = 150.2, 130.4, 129.3, 128.1, 75.7, 74.1,
60.9, 15.1.
Yellow oil. IR (neat): ν = 2215 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 7.51–7.64 (m, 2 H), 7.31–7.41 (m, 2 H), 7.18–
7.29 (m, 6 H). 13C NMR (75 MHz, CDCl3): δ = 134.7, 130.6,
129.37, 129.30, 129.1, 128.9, 126.7, 125.9, 98.5, 70.2.
(Oct-1-ynyl)(phenyl)sulfane (3l)
(2-Phenylethynyl)(p-tolyl)tellane (3p)
Orange oil. IR (neat): ν = 2210 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 7.27–7.59 (m, 9 H), 2.44 (s, 3 H). 13C NMR (75
MHz, CDCl3): δ = 131.7, 129.5, 129.1, 128.8, 128.4, 128.2,
127.0, 123.1, 100.8, 64.3, 22.9.
Yellow oil. IR (neat): ν = 2220 cm–1. 1H NMR (300 MHz,
CDCl3): δ = 7.58 (d, J = 8.6 Hz, 2 H), 7.27–7.37 (m, 3 H),
2.26 (t, J = 7.2 Hz, 2 H), 1.51 (quin, J = 7.4 Hz, 2 H), 1.21–
1.30 (m, 6 H), 0.86 (t, J = 6.5 Hz, 3 H). 13C NMR (75 MHz,
CDCl3): δ = 130.5, 129.7, 129.1, 126.7, 106.1, 61.7, 37.1,
31.5, 28.5, 22.5, 14.1.
Ethyl 3-(Phenyltellanyl)propiolate (3r)
Pale yellow oil. IR (neat): ν = 1674 cm–1. 1H NMR (300
MHz, CDCl3): δ = 7.35–7.36 (m, 5 H), 4.27 (q, J = 7.2 Hz, 2
H), 1.33 (t, J = 7.2 Hz, 3 H). 13C NMR (75 MHz, CDCl3):
δ = 149.9, 133.3, 129.3, 128.2, 74.1, 73.0, 60.5, 14.3.
Ethyl 3-(Phenylthio)propiolate (3n)
Colorless oil. IR (neat): ν = 1678 cm–1. 1H NMR (300 MHz,
Synlett 2014, 25, 1385–1390
© Georg Thieme Verlag Stuttgart · New York