99734-03-9Relevant academic research and scientific papers
Introducing deep eutectic solvents to polar organometallic chemistry: Chemoselective addition of organolithium and grignard reagents to ketones in air
Vidal, Cristian,Garcia-Alvarez, Joaquin,Hernan-Gomez, Alberto,Kennedy, Alan R.,Hevia, Eva
, p. 5969 - 5973 (2014)
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. Turning lithium green: A new protocol for the selective addition of Grignard and organolithium reagents to ketones in green, biorenewable, and deep eutectic solvents (DESs) is reported. The protocol establishes a bridge between main-group organometallic compounds and green solvents (ChCl=choline chloride; see picture). The DESs are superior reaction media for highly polar organometallic compounds.
Asymmetric Synthesis of α,α-Disubstituted Allylic Amines through Palladium-Catalyzed Allylic Substitution
Guo, Wusheng,Cai, Aijie,Xie, Jianing,Kleij, Arjan W.
supporting information, p. 11797 - 11801 (2017/09/06)
The first asymmetric synthesis of important α,α-disubstituted N-alkyl allyl amine scaffolds through allylic substitution is reported. This approach is based on palladium catalysis and features ample scope with respect to both the allylic precursor and amine reagent, and high asymmetric induction with enantiomeric ratios (e.r.) up to 98.5:1.5. The use of less-reactive anilines is also feasible, providing enantioenriched α,α-disubstituted N-aryl allylic amines.
