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Introducing Deep Eutectic Solvents to Polar Organometallic Chemistry: Chemoselective Addition of Organolithium and Grignard Reagents to Ketones in Air
Author(s) -
Vidal Cristian,
GarcíaÁlvarez Joaquín,
HernánGómez Alberto,
Kennedy Alan R.,
Hevia Eva
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201400889
Subject(s) - chemistry , reagent , reactivity (psychology) , organic chemistry , nucleophile , organic synthesis , halide , inert gas , eutectic system , inert , group 2 organometallic chemistry , combinatorial chemistry , molecule , catalysis , alloy , medicine , alternative medicine , pathology
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.