Exploiting deep eutectic solvents and organolithium reagent partnerships: chemoselective ultrafast addition to imines and quinolines under aerobic ambient temperature conditions

Cristian Vidal, Joaquín García-Álvarez, Alberto Hernán-Gómez, Alan R. Kennedy, Eva Hevia

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Shattering the long-held dogma that organolithium chemistry needs to be performed under inert atmospheres in toxic organic solvents, chemoselective addition of organolithium reagents to non-activated imines and quinolines has been accomplished in green, biorenewable deep eutectic solvents (DESs) at room temperature and in the presence of air, establishing a novel and sustainable access to amines. Improving on existing methods, this approach proceeds in the absence of additives; occurs without competitive enolization, reduction or coupling processes; and reactions were completed in seconds. Comparing RLi reactivities in DESs with those observed in pure glycerol or THF suggests a kinetic anionic activation of the alkylating reagents occurs, favoring nucleophilic addition over competitive hydrolysis.
LanguageEnglish
Pages16145-16148
Number of pages5
JournalAngewandte Chemie International Edition
Volume55
Issue number52
Early online date28 Nov 2016
DOIs
Publication statusPublished - 23 Dec 2016

Fingerprint

Quinolines
Imines
Eutectics
Temperature
Poisons
Glycerol
Organic solvents
Amines
Hydrolysis
Chemical activation
Atmosphere
Kinetics
Air

Keywords

  • organolithium chemistry
  • imines
  • organolithium reagents
  • quinolines
  • chemoselective addition
  • deep eutectic solvents
  • biorenewable
  • green chemistry
  • salt activation

Cite this

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title = "Exploiting deep eutectic solvents and organolithium reagent partnerships: chemoselective ultrafast addition to imines and quinolines under aerobic ambient temperature conditions",
abstract = "Shattering the long-held dogma that organolithium chemistry needs to be performed under inert atmospheres in toxic organic solvents, chemoselective addition of organolithium reagents to non-activated imines and quinolines has been accomplished in green, biorenewable deep eutectic solvents (DESs) at room temperature and in the presence of air, establishing a novel and sustainable access to amines. Improving on existing methods, this approach proceeds in the absence of additives; occurs without competitive enolization, reduction or coupling processes; and reactions were completed in seconds. Comparing RLi reactivities in DESs with those observed in pure glycerol or THF suggests a kinetic anionic activation of the alkylating reagents occurs, favoring nucleophilic addition over competitive hydrolysis.",
keywords = "organolithium chemistry, imines, organolithium reagents, quinolines, chemoselective addition, deep eutectic solvents, biorenewable, green chemistry, salt activation",
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Exploiting deep eutectic solvents and organolithium reagent partnerships : chemoselective ultrafast addition to imines and quinolines under aerobic ambient temperature conditions. / Vidal, Cristian; García-Álvarez, Joaquín; Hernán-Gómez, Alberto; Kennedy, Alan R.; Hevia, Eva.

In: Angewandte Chemie International Edition, Vol. 55, No. 52, 23.12.2016, p. 16145-16148.

Research output: Contribution to journalArticle

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