Chalcogenoacetylenes Obtained by Indium(III) Catalysis
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that the cross-coupling of diorgano diselenide with terminal
acetylenes is able to use both groups on the dichalcogenide.
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Conclusions
In conclusion, we have successfully developed a novel
and highly efficient procedure for synthesizing alkynyl chal-
cogenides in which dual activation of diorgano dichalcogen-
ides and terminal acetylenes is achieved by using an in-
dium(III) catalyst. This methodology is highly chemoselec-
tive, uses mild conditions, and allows the preparation of a
wide range of substituted alkynyl chalcogenides in one step
from readily available reagents. The synthetic applications
of this methodology as well as studies of the conditions for
the production of 1,2-diphenylseleno-1-alkenes by em-
ploying indium(III) salts are under investigation.
[2]
[3]
Experimental Section
General Procedure for the Synthesis of Alkynyl Chalcogenides 3: A
20-mL reaction tube was charged with diorgano dichalcogenide
(0.5 mmol), terminal acetylene (1.0 mmol), InCl3 (0.1 mmol),
Cs2CO3 (1.0 mmol), and dry DMSO (3.0 mL). The reaction vessel
was placed in an oil bath at 80 °C and stirred for 12 h. After com-
pletion of the reaction, the resulting mixture was cooled to room
temperature, diluted with Et2O, washed with brine (3ϫ15 mL) and
water (3ϫ15 mL), and dried with Na2SO4. The solvent was evapo-
rated, and the remaining oil was purified by column chromatog-
raphy (hexane/ethyl acetate, 99:1). All products were identified by
1H NMR, 13C NMR, and IR spectroscopy and mass spectrometry.
The spectral data of known compounds are in agreement with that
previously reported.
[4]
[5]
1
Phenyl(phenylethynyl)selane (3a): Yield 91%. H NMR (300 MHz,
CDCl3): δ = 7.63–7.11 (m, 10 H) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 136.5, 133.6, 131.8, 131.4, 131.2, 129.8, 129.5, 128.7,
[6]
[7]
128.2, 127.9, 127.6, 127.0, 105.0 ppm. IR (neat): ν = 3057, 2924,
˜
2160, 1576, 1489, 1439, 1068, 1022, 754, 688, 669 cm–1. MS (EI):
m/z = 258 [M]+.[5e]
J. V. Comasseto, P. H. Menezes, H. A. Stefani, G. Zeni, A. L.
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Supporting Information (see footnote on the first page of this arti-
cle): Experimental details; characterization data; and copies of the
1H NMR, 13C NMR, IR, and mass spectra of all compounds.
[8]
[9]
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Acknowledgments
We are grateful to CAPES (Coordenação de Aperfeiçoamento de
Pessoal de Nível Superior), CNPq (Conselho Nacional de Desen-
volvimento Científico e Tecnológico), INCT-CMN (Instituto Na-
cional de Ciência e Tecnologia de Catálise de Sistemas Moleculares
e Nanoestruturados) and FAPERGS (Fundação de Amparo a Pes-
quisa do Estado do Rio Grande do Sul) for financial support.
CNPq is also acknowledged for a Ph.D. fellowship to D. S. R.
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[1] For a comprehensive treatment of organoselenium chemistry,
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Org. Chem. 2009, 1649; b) T. G. Back, Organoselenium Chemis-
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Eur. J. Org. Chem. 2011, 7066–7070
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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