Silver Supported Nanoparticles on [Mg4 Al-LDH] as an Efficient Catalyst for the α-Alkylation of Nitriles, Oxindoles and Other Carboxylic Acid Derivatives with Alcohols.

An efficient heterogeneous silver-catalyzed α-alkylation of nitriles and oxindoles using alcohols via borrowing hydrogen strategy has been developed for the first time. The active nanostructured material, namely [Ag/Mg4 Al-LDH], composed by silver nanoparticles (3-4 nm average particle size) homogeneously stabilized onto a [Mg4 Al-LDH] support with suitable Brønsted basic properties, constitutes a stable catalyst for the sustainable building of novel C-C bonds from alcohols and C-nucleophiles. By applying this catalyst, a broad range of α-functionalized nitriles and oxindoles has been accessed with good to excellent isolated yields and without the addition of external bases. Moreover, the novel silver nanocatalyst has also demonstrated its successful application to the cyclization of N-[2-(hydroxymethyl)phenyl]-2-phenylacetamides to afford 3-arylquinolin-2(1H)-ones, through a one-pot dehydrogenation and intramolecular α-alkylation. Control experiments, kinetic studies, and characterization data of a variety of [Ag/LDH]-type materials confirmed the silver role in the dehydrogenation and hydrogenation steps, while [Mg4 Al-LDH] matrix is able to catalyze condensation. Interestingly, these studies suggest as key point for the successful activity of [Ag/Mg4 Al-LDH], in comparison with other [Ag/LDH]-type nanocatalysts, the suitable acid-base properties of this material.

Catalytic Reductive Alcohol Etherifications with Carbonyl-Based Compounds or CO2 and Related Transformations for the Synthesis of Ether Derivatives.

Ether derivatives have myriad applications in several areas of chemical industry and academia. Hence, the development of more effective and sustainable protocols for their production is highly desired. Among the different methodologies reported for ether synthesis, catalytic reductive alcohol etherifications with carbonyl-based moieties (aldehydes/ketones and carboxylic acid derivatives) have emerged in the last years as a potential tool. These processes constitute appealing routes for the selective production of both symmetrical and asymmetrical ethers (including O-heterocycles) with an increased molecular complexity. Likewise, ester-to-ether catalytic reductions and hydrogenative alcohol etherifications with CO2 to dialkoxymethanes and other acetals, albeit in less extent, have undergone important advances, too. In this Review, an update of the recent progresses in the area of catalytic reductive alcohol etherifications using carbonyl-based compounds and CO2 have been described with a special focus on organic synthetic applications and catalyst design. Complementarily, recent progress made in catalytic acetal/ketal-to-ether or ester-to-ether reductions and other related transformations have been also summarized.