Scheme 1. General Scheme of Synthesis of Diselenides
literature.14 Generally, catalysts in nanoscale afford a more
effective process and allow a genuine advance in relation to
traditional methodologies. The high surface area and reactive
morphologies of nanomaterials allow them to be effective
catalysts for organic synthesis.15
Figure 1. Various ways to prepare diselenides.
In this new intensive area, CuO has emerged as a useful
catalyst in several transformations.16 As previously reported,
CuO nanopowder shows an effective influence in the
chalcogenide functionalizations, allowing the synthesis of
organic selenides in high yields.17 As part of our ongoing
research into organochalcogen chemistry,18 herein we dis-
close a new and efficient methodology to prepare sym-
metrical aryl and alkyl diselenides and ditellurides using CuO
nanopowders as a catalyst, with good to excellent yields, as
depicted in Scheme 1.
variety of methods reported to prepare organic diselenides or
ditellurides (Figure 1). Most of them involve the reaction of
metal diselenides or ditellurides with alkyl halides, dimerization
with selenocyanates,5-7 oxidation of selenols8 or selenolates,9
and reactions of aldehydes with sodium hydrogen selenide
in the presence of an amine and sodium borohydride.10,11
Sonoda et al. discovered that elemental selenium can be
readily reduced by carbon monoxide and water in the
presence of base to produce hydrogen selenide, which was
successfully applied to the synthesis of aliphatic diselenides
from both aliphatic ketones and aldehydes12 or from alkyl
chlorides and acyl chlorides,13 respectively.
To the best of our knowledge, this is the first report of
the use of a CuO nanoparticle-catalyzed reaction to prepare
symmetrical organodichalcoganides.
In order to optimize the protocol and to understand the
influence of different variables in this reaction, several
components were studied. To this end, we carried out the
reaction under standard conditions employing 4-iodotoluene
Despite the variety of methodologies, there are some
drawbacks to these known methods of diselenide synthesis,
such as the use of strong reducing agents, highly toxic gas,
harsh reaction conditions, low yields, or complex manipula-
tions. From a sustainable chemistry point of view, there is a
need for new methods that are truly efficient, high yielding,
responsive to mild reaction conditions, byproduct-free, and
efficient in the presence of multifunctional groups. Organic
reactions catalyzed by metallic nanostructures are currently
an area of intensive research, with many reports in the
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