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

Abstract

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.

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“…Both dry and sol-gel methods can be used in hydride reduction. In the dry method, pristine TiO 2 and hydride are mixed and annealed in Ar and N 2 atmosphere [ 151 ]. In the sol-gel process, NaBH 4 is used as the reduction agent.…”

Biomass-Modified Zirconium-Based Catalyst for One-Pot Reductive Etherification of Bioderived Aldehydes to Furanic Diether

“…HMF can be transformed by hydrogenolysis to 2,5-dimethyl furan which is often used as a fuel additive. 13 Furan can also be upgraded to produce liquid fuel by many methods such as Friedel−Crafts alkylation with arenes, 14,15 aldol condensation with ketones, 16 and Baylis−Hillman reactions between methylacrylate and HMF. 17 Another way to convert HMF to biodiesel components is to direct convert it to ethers, which can be used directly as fuels or fuel additives because ethers possess excellence miscibility with diesel, a high cetane number, and high energy density.…”

“…HMF can be transformed by hydrogenolysis to 2,5-dimethyl furan which is often used as a fuel additive . Furan can also be upgraded to produce liquid fuel by many methods such as Friedel–Crafts alkylation with arenes, , aldol condensation with ketones, and Baylis–Hillman reactions between methylacrylate and HMF …”