Introducing glycerol as a sustainable solvent to organolithium chemistry: ultrafast chemoselective addition of aryllithium reagents to nitriles under air and at ambient temperature

María J. Rodríguez-Álvarez, Joaquín García-Álvarez, Marina Uzelac, Michael Fairley, Charles T. O'Hara, Eva Hevia

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11 Citations (Scopus)

Abstract

Edging closer towards developing air and moisture compatible polar organometallic chemistry, the chemoselective and ultrafast addition of a range of aryllithium reagents to nitriles has been accomplished using glycerol as a solvent, at ambient temperature in the presence of air, establishing a novel sustainable access to aromatic ketones. Addition reactions occur heterogeneously ("on glycerol conditions"), where the lack of solubility of the nitriles in glycerol and the ability of the latter to form strong intermolecular H-bonds seem key to favouring nucleophilic addition over competitive hydrolysis. Remarkably, PhLi exhibits a greater resistance to hydrolysis working "on glycerol" conditions than "on water". Introducing glycerol as a new solvent in organolithium chemistry unlocks a myriad of opportunities for developing more sustainable, air and moisture tolerant main-group-metal-mediated organic synthesis.
LanguageEnglish
Number of pages7
JournalChemistry - A European Journal
Early online date27 Nov 2017
DOIs
Publication statusE-pub ahead of print - 27 Nov 2017

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Nitriles
Glycerol
Air
Hydrolysis
Moisture
Temperature
Addition reactions
Organometallics
Ketones
Solubility
Metals
Water

Keywords

  • organolithium reagents
  • glycerol
  • water
  • green chemistry
  • nitriles

Cite this

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title = "Introducing glycerol as a sustainable solvent to organolithium chemistry: ultrafast chemoselective addition of aryllithium reagents to nitriles under air and at ambient temperature",
abstract = "Edging closer towards developing air and moisture compatible polar organometallic chemistry, the chemoselective and ultrafast addition of a range of aryllithium reagents to nitriles has been accomplished using glycerol as a solvent, at ambient temperature in the presence of air, establishing a novel sustainable access to aromatic ketones. Addition reactions occur heterogeneously ({"}on glycerol conditions{"}), where the lack of solubility of the nitriles in glycerol and the ability of the latter to form strong intermolecular H-bonds seem key to favouring nucleophilic addition over competitive hydrolysis. Remarkably, PhLi exhibits a greater resistance to hydrolysis working {"}on glycerol{"} conditions than {"}on water{"}. Introducing glycerol as a new solvent in organolithium chemistry unlocks a myriad of opportunities for developing more sustainable, air and moisture tolerant main-group-metal-mediated organic synthesis.",
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author = "Rodr{\'i}guez-{\'A}lvarez, {Mar{\'i}a J.} and Joaqu{\'i}n Garc{\'i}a-{\'A}lvarez and Marina Uzelac and Michael Fairley and O'Hara, {Charles T.} and Eva Hevia",
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AU - Rodríguez-Álvarez, María J.

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AU - Uzelac, Marina

AU - Fairley, Michael

AU - O'Hara, Charles T.

AU - Hevia, Eva

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AB - Edging closer towards developing air and moisture compatible polar organometallic chemistry, the chemoselective and ultrafast addition of a range of aryllithium reagents to nitriles has been accomplished using glycerol as a solvent, at ambient temperature in the presence of air, establishing a novel sustainable access to aromatic ketones. Addition reactions occur heterogeneously ("on glycerol conditions"), where the lack of solubility of the nitriles in glycerol and the ability of the latter to form strong intermolecular H-bonds seem key to favouring nucleophilic addition over competitive hydrolysis. Remarkably, PhLi exhibits a greater resistance to hydrolysis working "on glycerol" conditions than "on water". Introducing glycerol as a new solvent in organolithium chemistry unlocks a myriad of opportunities for developing more sustainable, air and moisture tolerant main-group-metal-mediated organic synthesis.

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