Abstract After a long adolescence, the chemistry of lithium carbenoids has currently been entering its maturity bringing dowry more in‐depth and less empirical knowledge structure configurational stability such double‐faced intermediates; this, thanks in particular to synergistic harmonic cooperation between calculations most modern NMR techniques now at our disposal. Such stimulated development fruitful stereoselective applications field organic synthesis, providing addition rationale...

Grignard and organolithium reagents undergo smooth nucleophilic additions to γ-chloroketones “on water”.

Abstract Developing new green solvents in designing chemical products and processes or successfully employing the already existing ones is one of key subjects chemistry especially important organometallic chemistry, which an interdisciplinary field. Can we advantageously also use unconventional reaction media place current harsh organic for polar compounds? This microreview critically analyses state art with regard to this topic showcases recent developments breakthroughs that are becoming...

There is a strong imperative to reduce the release of volatile organic compounds (VOCs) into environment, and many efforts are currently being made replace conventional hazardous VOCs in favour safe, green bio-renewable reaction media that not based on crude petroleum. Recent ground-breaking studies from few laboratories worldwide have shown both Grignard (functionalised) organolithium reagents, traditionally handled under strict exclusion air humidity anhydrous VOCs, can smoothly promote...

Different metal-free catalytic enantioselective reactions have been performed in high yields and enantioselectivity natural, biorenewable environmentally-friendly DESs. The recyclability of the chiral catalyst by a simple extraction protocol was also successfully accomplished.

Transition-metal complexes and purified ketoreductases work together in eutectic mixtures for the synthesis of enantiopure secondary alcohols.

Abstract Dye‐sensitized solar cells (DSSCs) that use an aqueous (40 % w / water content) choline chloride based deep eutectic solvent as electrolyte medium have been investigated. The joint combination of the mixture and appropriate hydrophilic sensitizer afforded a DSSC with power conversion efficiency comparable to using same composition but conventional, toxic, volatile solvents medium, which thereby paves way new generation eco‐friendly, nature‐inspired, low‐cost devices.

In contrast to classic methods carried out under inert atmospheres with dry volatile organic solvents and often low temperatures, the addition of highly polar organometallic compounds non-activated imines nitriles proceeds quickly, efficiently, chemoselectively a broad range substrates at room temperature air water as only reaction medium. Secondary amines tertiary carbinamines are furnished in yields up over 99 %. The significant solvent D/H isotope effect observed for on-water nucleophilic...

<italic>ortho</italic>-Lithiation/functionalization of diaryltetrahydrofurans proceeds well with <italic>t</italic>-BuLi both in Et₂O and cyclopentyl methyl ether and, remarkably, also protic eutectic mixtures.

Abstract In this contribution, we report the first successful baker's yeast reduction of arylpropanones using deep eutectic solvents (DESs) as biodegradable and non‐hazardous co‐solvents. The nature DES [ e.g . choline chloride/glycerol (2:1)] percentage water in mixture proved to be critical for both reversal selectivity achieve high enantioselectivity on going from pure (up 98:2 er favour S ‐enantiomer) DES/aqueous mixtures R ‐enantiomer). As a result, enantiomers valuable chiral alcohols...

Functionalised primary alcohols can be obtained by a novel highly regioselective THF ring-opening transformation, which takes place from laterally lithiated intermediates, under air, and in glycerol-based eutectic mixture.

A new series of multifunctional hybrids, based on the structure donepezil (DNP) drug, have been developed and evaluated as potential anti Alzheimer's disease (AD) agents. The rationale this study was conjugation a benzylpiperidine/benzylpiperazine moiety with derivatives bioactive heterocyclics (benzimidazole or benzofuran), to mimic main DNP endow hybrids additional relevant properties such inhibition amyloid beta (Aβ) peptide aggregation, antioxidant activity metal chelation. Overall, they...

A palladium-catalysed aminocarbonylation of (hetero)aryl iodides has, for the first time, been accomplished in deep eutectic solvents as environmentally benign and recyclable media, under mild conditions. The reactions proceeded with a good substrate scope, variety amides have synthesized yields up to 98%.

Abstract Pd‐catalyzed Suzuki–Miyaura cross‐coupling between (hetero)aryl halides (Cl, Br, I) and versatile, moisture‐stable mono‐ bifunctional potassium aryltrifluoroborates proceeded efficiently chemoselectively in air under generally mild conditions; a catalyst loading as low 1 mol % combined with Na 2 CO 3 base choline chloride/glycerol (1:2) deep eutectic solvent (DES) was used sustainable environmentally responsible medium. The catalyst, base, DES were easily successfully recycled up to...

Abstract Direct palladium‐catalysed cross‐couplings between organolithium reagents and (hetero)aryl halides (Br, Cl) proceed fast, cleanly selectively at room temperature in air, with water as the only reaction medium presence of NaCl a cheap additive. Under optimised conditions, water‐accelerated catalysis is responsible for furnishing C(sp 3 )–C(sp 2 ), C(sp)–C(sp ) cross‐coupled products, competition protonolysis, within time 20 s, yields up to 99 %, absence undesired...

Transition-metal complexes and polarised organometallic reagents play together in <italic>Deep Eutectic Solvents</italic>.

Abstract The commercially available and cheap Pd/C was found to promote Sonogashira couplings in the environmentally friendly choline chloride/glycerol eutectic mixture absence of external ligands. Under heterogeneous conditions, (hetero)aryl iodides were successfully coupled with both aromatic aliphatic alkynes yields ranging from 50 99 % within 3 h at 60 °C. aforementioned catalytic system proved be effective also towards electron‐rich iodides, which are notoriously known poorly reactive...

Directed ortho metalation (DoM) or nucleophilic acyl substitution (SNAc) can be efficiently programmed on the same aromatic carboxylic acid amide, in a choline chloride-based eutectic mixture, by simply switching nature of organolithium reagent. Telescoped, one-pot ortho-lithiation/Suzuki-Miyaura cross-couplings have also been demonstrated for first time Deep Eutectic Solvents.

Abstract Pd‐catalyzed Negishi cross‐coupling reactions between organozinc compounds and (hetero)aryl bromides have been reported when using bulk water as the reaction medium in presence of NaCl or biodegradable choline chloride/urea eutectic mixture. Both C(sp 3 )‐C(sp 2 ) couplings found to proceed smoothly, with high chemoselectivity, under mild conditions (room temperature 60 °C) air, competition protonolysis. Additional benefits include very short times (20 s), good excellent yields (up...

Polymeric materials are widely used in every human endeavor (bottles, clothes, containers, toys, tools, etc.) due to their unique properties of chemical and mechanical resistance. They are, however, almost non-biodegradable, recycling into monomers is difficult costly, thereby allowing accumulation the environment. This review highlights recent advances use deep eutectic solvents (DESs) as catalysts and/or green plastics degradation, with aim designing greener processes for polymers’...