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

Department of Chemistry

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

56 Citations (SciVal)

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 by 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 hydrogen 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
Pages (from-to)	1720-1725
Number of pages	6
Journal	Chemistry - A European Journal
Volume	24
Issue number	7
DOIs	https://doi.org/10.1002/chem.201705577
Publication status	Published - 1 Feb 2018

Bibliographical note

Funding Information:
We are indebted to the MINECO of Spain (Projects CTQ2014-51912-REDC and CTQ2016-75986-P), the Gobierno del Principa-do de Asturias (Project GRUPIN14-006) and the Fundación BBVA for the award of a “Beca Leonardo a Investigadores y Creadores Culturales 2017” to J.G.A.[32] We also thank the EPSRC (EP/N011384/1) and the Society of Spanish Researchers in the UK (SRUK) and the Fundación Santander (Emerging Talent Award to E.H.). The Scottish Funding Council are thanked for a PECRE award to M.F. to enable an exchange visit to Oviedo University. The dataset underlying this research can be located at https://doi.org/10.15129/d260e1b4-64f2-4c6d-8076-cff2748fec2b.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Funding

We are indebted to the MINECO of Spain (Projects CTQ2014-51912-REDC and CTQ2016-75986-P), the Gobierno del Principa-do de Asturias (Project GRUPIN14-006) and the Fundación BBVA for the award of a “Beca Leonardo a Investigadores y Creadores Culturales 2017” to J.G.A.[32] We also thank the EPSRC (EP/N011384/1) and the Society of Spanish Researchers in the UK (SRUK) and the Fundación Santander (Emerging Talent Award to E.H.). The Scottish Funding Council are thanked for a PECRE award to M.F. to enable an exchange visit to Oviedo University. The dataset underlying this research can be located at https://doi.org/10.15129/d260e1b4-64f2-4c6d-8076-cff2748fec2b.

Keywords

glycerol
green chemistry
nitriles
organolithium reagents
water

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.201705577

Cite this

Rodríguez-Álvarez, M. J., García-Álvarez, J., Uzelac, M., Fairley, M., O'Hara, C. T., & Hevia, E. (2018). 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, 24(7), 1720-1725. https://doi.org/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. / Rodríguez-Álvarez, María J.; García-Álvarez, Joaquín; Uzelac, Marina et al.
In: Chemistry - A European Journal, Vol. 24, No. 7, 01.02.2018, p. 1720-1725.

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

Rodríguez-Álvarez, MJ, García-Álvarez, J, Uzelac, M, Fairley, M, O'Hara, CT & Hevia, E 2018, '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, vol. 24, no. 7, pp. 1720-1725. 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 by 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 hydrogen 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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Introducing Glycerol as a Sustainable Solvent to Organolithium Chemistry: Ultrafast Chemoselective Addition of Aryllithium Reagents to Nitriles under Air and at Ambient Temperature

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

Access to Document

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