Introducing deep eutectic solvents to polar organometallic chemistry : chemoselective addition of organolithium and grignard reagents to ketones in air

Vidal, Cristian and Garcia Alvarez, Joaquin and Hernán-Gómez, Alberto and Kennedy, Alan R and Hevia, Eva (2014) Introducing deep eutectic solvents to polar organometallic chemistry : chemoselective addition of organolithium and grignard reagents to ketones in air. Angewandte Chemie International Edition, 53 (23). 5969–5973.

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    Abstract

    Despite their enormous synthetic relevance, the use of polar organolithium and Grignard reagents is greatly limited by their requirements of low temperatures in order to control their reactivity as well as the need of dry organic solvents and inert atmosphere protocols to avoid their fast decomposition. Breaking new ground on the applications of these commodity organometallics in synthesis under more environmentally friendly conditions, this work introduces deep eutetic solvents (DESs) as a green alternative media to carry out chemoselective additions of ketones in air at room temperature. Comparing their reactivities in DES with those observed in pure water suggest that a kinetic activation of the alkylating reagents is taking place, favoring nucleophilic addition over the competitive hydrolysis, which can be rationalized through formation of halide-rich magnesiate or lithiate species.