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

Rodríguez-Álvarez, María J. and García-Álvarez, Joaquín and Uzelac, Marina and Fairley, Michael and O'Hara, Charles T. and Hevia, Eva (2017) Introducing glycerol as a sustainable solvent to organolithium chemistry : ultrafast chemoselective addition of aryllithium reagents to nitriles under air and at ambient temperature. Chemistry - A European Journal. ISSN 0947-6539

[img]
Preview
Text (Rodriguez-Alvarez-etal-CEJ2017-Introducing-glycerol-as-a-sustainable-solvent-to-organolithium-chemistry)
Rodriguez_Alvarez_etal_CEJ2017_Introducing_glycerol_as_a_sustainable_solvent_to_organolithium_chemistry.pdf
Accepted Author Manuscript

Download (1MB)| Preview

    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.