ic7b01576_si_001.pdf (2.15 MB)
Facile Access to Amides from Oxygenated or Unsaturated Organic Compounds by Metal Oxide Nanocatalysts Derived from Single-Source Molecular Precursors
journal contribution
posted on 2017-08-21, 16:05 authored by Akbar Mohammad, Prakash Chandra, Topi Ghosh, Mauro Carraro, Shaikh M. MobinOxidative
amidation is a valuable process for the transformation of oxygenated
organic compounds to valuable amides. However, the reaction is severely
limited by the use of an expensive catalyst and limited substrate
scope. To circumvent these limitations, designing a transition-metal-based
nanocatalyst via more straightforward and economical methodology with
superior catalytic performances with broad substrate scope is desirable.
To resolve the aforementioned issues, we report a facile method for
the synthesis of nanocatalysts NiO and CuO by the sol–gel-assisted
thermal decomposition of complexes [Ni(hep-H)(H2O)4]SO4 (SSMP-1) and [Cu(μ-hep)(BA)]2 (SSMP-2) [hep-H = 2-(2-hydroxylethyl)pyridine;
BA = benzoic acid] as single-source molecular precursors (SSMPs) for
the oxidative amidation of benzyl alcohol, benzaldehyde, and BA by
using N,N-dimethylformamide (DMF)
as the solvent and as an amine source, in the presence of tert-butylhydroperoxide (TBHP) as the oxidant, at T = 80 °C. In addition to nanocatalysts NiO and CuO,
our previously reported Co/CoO nanocatalyst (CoNC), derived from the
complex [CoII(hep-H)(H2O)4]SO4 (A) as an SSMP, was also explored for the aforementioned
reaction. Also, we have carefully investigated the difference in the
catalytic performance of Co-, Ni-, and Cu-based nanoparticles synthesized
from the SSMP for the conversion of various oxygenated and unsaturated
organic compounds to their respective amides. Among all, CuO showed
an optimum catalytic performance for the oxidative amidation of various
oxygenated and unsaturated organic compounds with a broad reaction
scope. Finally, CuO can be recovered unaltered and reused for several
(six times) recycles without any loss in catalytic activity.