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

Cristian Vidal, Joaquin Garcia Alvarez, Alberto Hernán-Gómez, Alan R Kennedy, Eva Hevia

Research output: Contribution to journalArticle

83 Citations (Scopus)

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.

LanguageEnglish
Pages5969–5973
Number of pages5
JournalAngewandte Chemie International Edition
Volume53
Issue number23
Early online date25 Apr 2014
DOIs
Publication statusPublished - 2 Jun 2014

Fingerprint

Organometallics
Ketones
Eutectics
Air
Organic solvents
Hydrolysis
Chemical activation
Decomposition
Temperature
Kinetics
Water

Keywords

  • addition reactions
  • deep eutectic solvents
  • green chemistry
  • Grignard reagents
  • organolithium compounds

Cite this

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Introducing deep eutectic solvents to polar organometallic chemistry : chemoselective addition of organolithium and grignard reagents to ketones in air. / Vidal, Cristian; Garcia Alvarez, Joaquin; Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva.

In: Angewandte Chemie International Edition, Vol. 53, No. 23, 02.06.2014, p. 5969–5973.

Research output: Contribution to journalArticle

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