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

doi:10.1002/chem.201705577

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

Pure And Applied Chemistry

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55 Citations (Scopus)

115 Downloads (Pure)

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.

Original language	English
Number of pages	7
Journal	Chemistry - A European Journal
Early online date	27 Nov 2017
DOIs	https://doi.org/10.1002/chem.201705577
Publication status	E-pub ahead of print - 27 Nov 2017

Keywords

organolithium reagents
glycerol
water
green chemistry
nitriles

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10.1002/chem.201705577

Rodriguez-Alvarez-etal-CEJ2017-Introducing-glycerol-as-a-sustainable-solvent-to-organolithium-chemistryAccepted author manuscript, 1.28 MB

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Rodríguez-Álvarez, M. J., García-Álvarez, J., Uzelac, M., Fairley, M., O'Hara, C. T., & 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. Advance online publication. 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. ",

keywords = "organolithium reagents, glycerol, water, green chemistry, nitriles",

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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language = "English",

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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.; García-Álvarez, Joaquín; Uzelac, Marina et al.
In: Chemistry - A European Journal, 27.11.2017.

Research output: Contribution to journal › Article › peer-review

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AU - Rodríguez-Álvarez, María J.

AU - García-Álvarez, Joaquín

AU - Uzelac, Marina

AU - Fairley, Michael

AU - O'Hara, Charles T.

AU - Hevia, Eva

N1 - 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.

PY - 2017/11/27

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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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JF - Chemistry - A European Journal

ER -

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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Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry

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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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Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry

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