The Future of Polar Organometallic Chemistry Written in Bio‐Based Solvents and Water

Abstract

There is a strong imperative to reduce the release of volatile organic compounds (VOCs) into the environment, and many efforts are currently being made to replace conventional hazardous VOCs in favour of safe, green and bio-renewable reaction media that are not based on crude petroleum. Recent ground-breaking studies from a few laboratories worldwide have shown that both Grignard and (functionalised) organolithium reagents, traditionally handled under strict exclusion of air and humidity and in anhydrous VOCs, can smoothly promote both nucleophilic additions to unsaturated substrates and nucleophilic substitutions in water and other bio-based solvents (glycerol, deep eutectic solvents), competitively with protonolysis, at room temperature and under air. The chemistry of polar organometallics in the above protic media is a complex phenomenon influenced by several factors, and understanding its foundational character is stimulating in the perspective of the development of a sustainable organometallic chemistry.

Effective Release of Intracellular Enzymes by Permeating the Cell Membrane with Hydrophobic Deep Eutectic Solvents

“…The interactions between HBAs and HBDs are hydrogen bonds and the physicochemical properties of the DESs can be customized by altering the components. DESs have been used in a wide range of applications, such as extraction, biocatalysis, carbon dioxide capture, and biomedical applications . Most of the early DESs studied were hydrophilic, which limited their application with aqueous samples.…”

Positive Impact of Natural Deep Eutectic Solvents on the Biocatalytic Performance of 5-Hydroxymethyl-Furfural Oxidase

“…These compounds show high diversity, are biodegradable and present very low toxicology, making them also attractive for pharmaceutical purposes. In the last few years, the applicability of (NA)DES has been demonstrated for organic extractions [22,23], for electrochemical purposes [24] and in catalytic procedures [25,26] Regarding this last application, DESs have been employed as solvents, cosolvents, additives or supports to anchor catalysts and/or solvents in a catalytic process.…”

DESign of Sustainable One-Pot Chemoenzymatic Organic Transformations in Deep Eutectic Solvents for the Synthesis of 1,2-Disubstituted Aromatic Olefins

“…In this context and during the last decade, a new family of sustainable reaction media, the socalled Deep Eutectic Solvents (DESs) (Abbott et al, 2003(Abbott et al, , 2004 has attracted the attention of many research groups worldwide. As consequence, these neoteric solvents have been broadly applied in chemistry as sustainable reaction media for: (i) polar organometallic chemistry (Mallardo et al, 2014;Vidal et al, 2014Vidal et al, , 2016Sassone et al, 2015;García-Álvarez et al, 2018;Rodríguez-Álvarez et al, 2018;Ghinato et al, 2019); (ii) metal catalyzed organic reactions (García-Álvarez, 2015; Vidal and García-Álvarez, 2019); (iii) biocatalysis (Gotor-Fernández and Paul, 2018); (iv) traditional organic synthesis (Liu et al, 2015;Alonso et al, 2016); (v) metal extraction and electrochemistry (Smith et al, 2014;Millia et al, 2018); and (v) polymer science (Carriazo et al, 2012;del Monte et al, 2014;Mota-Morales et al, 2018;Quirós-Montes et al, 2019;Roda et al, 2019;Sánchez-Condado et al, 2019). These sustainable eutectic solvents can be obtained just by mixing (without any further steps of purification or isolation) two molecules capable of forming a complex intermolecular network based on hydrogenbond interactions.…”