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The crude products were transferred and the solid washed with
CH2Cl2 (3 Â 10 mL) and water (3 Â 10 mL). The desired product
was extracted in organic phase, washed with H2O three times
and finally dried (Na2SO4). Impure products were purified by
flash chromatography on silica gel (hexane–EtOAc). Products
1
were analysed using H NMR and 13C NMR spectroscopy, MS
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Conclusions
Despite its apparent simplicity, the reduction of nitro com-
pounds constitutes a key and venerable transformation, which
extends its importance to the chemical industry. Even though
numerous papers and patents have reported on the reduction
of nitro derivatives with variable success, selective reduction at
the nitro group is not easy to make in the presence of other
competing functionalities. In conclusion, we have developed a
facile new protocol for selective reduction of nitro and azido
derivatives that utilises the, mostly unexplored, mechano-
chemical approach. To best of our knowledge, no report has
so far described hydrogenation without catalyst addition being
performed in a ball mill. This method benefits from the use of
convenient, cost-effective, environmentally friendly formate
salts as hydrogen donors. The mechanochemical approach is
efficient, versatile with short reaction times and high yields,
taking advantage by the easy workup. Challenging functional
groups, such as –I, –Br, –Cl, –CO and –COMe, were well tolerated
under the described reaction conditions. The advantages of our
method include its metal-free nature, its use of eco-friendly and
easily available formate salts as the hydrogen source and the
ambient reaction conditions.
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Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
Authors acknowledge the University of Turin for the financial
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This journal is ©The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018 New J. Chem., 2018, 42, 18881--18888 | 18887