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

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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 1521-3765 (https://doi.org/10.1002/chem.201705577)

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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.

ORCID iDs

Rodríguez-Álvarez, María J., García-Álvarez, Joaquín, Uzelac, Marina ORCID logoORCID: https://orcid.org/0000-0002-5060-7017, Fairley, Michael ORCID logoORCID: https://orcid.org/0000-0002-6021-0339, O'Hara, Charles T. and Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506;
  • Item type:Article
    ID code:62486
    Dates:
    Date
    Event
    27 November 2017
    Published
    27 November 2017
    Published Online
    24 November 2017
    Accepted
    Notes:This is the peer reviewed version of the following article: Rodríguez-Álvarez, MJ, García-Álvarez, J, Uzelac, M, Fairley, M, O'Hara, CT & Hevia, E 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., which has been published in final form at https://doi.org/10.1002/chem.201705577. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:30 Nov 2017 12:03
    Last modified:11 Nov 2024 11:51
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/62486
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