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

Vidal, Cristian and García-Álvarez, Joaquín and Hernán-Gómez, Alberto and Kennedy, Alan R. and Hevia, Eva (2016) Exploiting deep eutectic solvents and organolithium reagent partnerships : chemoselective ultrafast addition to imines and quinolines under aerobic ambient temperature conditions. Angewandte Chemie International Edition, 55 (52). pp. 16145-16148. ISSN 1433-7851

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    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.