Exploiting Deep Eutectic Solvents and Organolithium Reagent Partnerships: Chemoselective Ultrafast Addition to Imines and Quinolines Under Aerobic Ambient Temperature Conditions

Vidal, Cristian; García‐Álvarez, Joaquín; Hernán‐Gómez, Alberto; Kennedy, Alan R.; Hevia, Eva

doi:10.1002/anie.201609929

Cited by 129 publications

(66 citation statements)

References 27 publications

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“…What was thought impossible just a few years ago, an aerobic, sustainable, polar, organometallic chemistry, is now starting to look distinctly possible . Thus, we recently uncovered the potential of deep eutectic solvents (DESs) by utilizing the nontoxic and biorenewable ammonium salt choline chloride [ChCl, (Me 3 NCH 2 CH 2 OH) + Cl − ] as an unique and green reaction medium for chemoselective ketone alkylation/arylation with organolithium or Grignard reagents at room temperature under air (Scheme ) . Comparing these reactions in DESs with those in neat water revealed a kinetic activation in the former, favoring addition reactions over hydrolysis.…”

Section: Introductionsupporting

confidence: 85%

Organolithium‐Initiated Polymerization of Olefins in Deep Eutectic Solvents under Aerobic Conditions

et al. 2019

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Despite their ubiquitous presence in synthesis, the use of polar organolithium reagents under environmentally benign conditions constitutes one of the greatest challenges in sustainable chemistry. Their high reactivity imposes the use of severely restrictive protocols (e.g., moisture‐ and oxygen‐free, toxic organic solvents, inert atmospheres, low temperatures, etc.). Making inroads towards meeting this challenge, a new air‐ and moisture‐compatible organolithium‐mediated methodology for the anionic polymerization of different olefins (e.g., styrenes and vinylpyridines) was established by pioneering the use of deep eutectic solvents (DESs) as an eco‐friendly reaction medium in this type of transformation. Fine‐tuning of the conditions (sonication of the reaction mixture at 40 °C in the absence of protecting atmosphere) along with careful choice of components of the DES [choline chloride (ChCl) and glycerol (Gly) in a 1:2 ratio] furnished the desired organic polymers (homopolymers and random copolymers) in excellent yields (up to 90 %) and low polydispersities (IPD 1.1–1.3). Remarkably, the in situ‐formed polystyril lithium intermediates exhibited a great resistance to hydrolysis in the eutectic mixture 1ChCl/2Gly (up to 1.5 h), hinting at an unexpected high stability of these otherwise highly reactive organolithium species in these unconventional reaction media. This unique stability can be exploited to create well defined block‐copolymers.

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Section: Introductionsupporting

confidence: 85%

Organolithium‐Initiated Polymerization of Olefins in Deep Eutectic Solvents under Aerobic Conditions

et al. 2019

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“…Thus, advancing the fundamental knowledge on DES structuring, and solvent‐reagent interactions will be the key in order to make further progress in the synthetic applications of polar organometallics in these unconventional solvents. More recently, by expanding the scope of these type chemistry in DESs, Hevia and García‐Álvarez have reported the addition reaction of a wide range of organolithium reagents to non‐activated imines . In this study, better conversions are observed using a 1:2 mixture of ChCl and glycerol ( Gly ) (Scheme ).…”

Section: Introducing Deep Eutectic Solvents To Polar Organometallic Cmentioning

confidence: 69%

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

García‐Álvarez

Hevia

Capriati

2018

Chemistry A European J

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111

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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.

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“…[142] Scheme 30. [155,156] Furthermore, palladium catalyzed C-C coupling reactions were performed in DES based on saccharides and DMU or urea, including the Stille, [157] Heck, Sonogashira, [158] and Suzuki [159] coupling. [142] As mentioned above, the Diels-Alder reaction was performed in Lewis-acidic ILs, namely [bpy][AlCl 4 ] and [emim][AlCl 4 ].…”

Section: Application In Organic Synthesismentioning

confidence: 99%

Organic Synthesis without Conventional Solvents

Obst

König

2018

Eur J Org Chem

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Organic synthesis without an organic solvent is still the exception. In this microreview, we discuss and compare different synthetic methods that proceed in the absence of conventional organic solvents. This includes solvent‐free methods in solids (mechanochemistry and solid‐state photochemistry), and in neat liquids (thermal and photocatalytic), as well as the application of unconventional solvents, such as ionic liquids and deep‐eutectic solvents. The different approaches are briefly introduced and examples illustrate their specific advantages, followed by a critical discussion of their limitations. Some methods have the intrinsic benefits of solvent‐free operation, such as avoiding solubility problems and side‐reactions with the solvent. However, every method has specific advantages and the demand of the synthetic application is crucial for selecting the best technique.

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Exploiting Deep Eutectic Solvents and Organolithium Reagent Partnerships: Chemoselective Ultrafast Addition to Imines and Quinolines Under Aerobic Ambient Temperature Conditions

Cited by 129 publications

References 27 publications

Organolithium‐Initiated Polymerization of Olefins in Deep Eutectic Solvents under Aerobic Conditions

Organolithium‐Initiated Polymerization of Olefins in Deep Eutectic Solvents under Aerobic Conditions

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

Organic Synthesis without Conventional Solvents

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