The search for sustainable alternatives for use in chemical synthesis and catalysis has found an ally in non-conventional energy sources and widely available green solvents. The use of glycerol, an abundant natural solvent, as an excellent "sacrificial" hydrogen source for the copper-catalyzed microwave (MW)-promoted transfer hydrogenation of nitrobenzene to aniline has been investigated in this work. Copper nanoparticles (CuNPs) were prepared in glycerol and the efficacy of the glycerol layer in mediating the interaction between the metal active sites has been examined using HRTEM analyses. Its high polarity, low vapor pressure, long relaxation time, and high acoustic impedance mean that excellent results were also obtained when the reaction media was subjected to ultrasound (US) and MW irradiation. US has been shown to play an important role in the process via its ability to enhance CuNPs dispersion, favor mechanical depassivation and increase catalytic active surface area, while MW irradiation shortened the reaction time from some hours to a few minutes. These synergistic combinations promoted the exhaustive reduction of nitrobenzene to aniline and facilitated the scale-up of the protocol for its optimized use in industrial MW reactors.
The use of copper(0) nanoparticles in the transfer semihydrogenation of alkynes has been investigated as a lead‐free alternative to Lindlar catalysts. A stereo‐selective methodology for the hydrogenation of internal alkynes to the corresponding (Z)‐alkenes in high isolated yields (86% average) has been developed. This green and sustainable transfer hydrogenation protocol relies on non‐noble copper nanoparticles for reduction of both electron‐rich and electron‐deficient, aliphatic‐substituted and aromatic‐ substituted internal alkynes. Polyols, such as ethylene glycol and glycerol, have been proven to act as hydrogen sources, and excellent stereo‐ and chemoselectivity have been observed. Enabling technologies, such as microwave and ultrasound irradiation are shown to enhance heat and mass transfer, whether used alone or in combination, resulting in a decrease in reaction time from hours to minutes.
Silica-supported metallic species have emerged as valuable green-chemistry catalysts because their high efficiency enables a wide range of applications, even at industrial scales. As a consequence, the preparation of these systems needs to be finely controlled in order to achieve the desired activity. The present work presents a detailed investigation of an ultrasound-promoted synthetic protocol for the grafting of β-cyclodextrin (β-CD) onto silica. Truly, ultrasound irradiation has emerged as a fast technique for promoting efficient derivatization of a silica surface with organic moieties at low temperature. Three different β-CD silica-grafted derivatives have been obtained, and the ability of β-CD to direct and bind Cu when CD is bonded to silica has been studied. A detailed characterization has been performed using TGA, phenolphthalein titration, FT-IR, diffuse reflectance (DR), DR UV-Vis, as well as the inductively-coupled plasma (ICP) of the β-CD silica-grafted systems and the relative Cu-supported catalysts. Spectroscopic characterization monitored the different steps of the reaction, highlighting qualitative differences in the properties of amino-derivatized precursors and final products. In order to ensure that the Cu-β-CD silica catalyst is efficient and robust, its applicability in Cu(II)-catalyzed alkyne azide reactions in the absence of a reducing agent has been explored. The presence of β-CD and an amino spacer has been shown to be crucial for the reactivity of Cu(II), when supported.
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