NDLI: Derivatization of (quinolin-8-yl)phosphinimidic amides via ortho-lithiation revisited

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Fernández Sáez, Nerea García López, Jesús López Ortiz, Fernando Iglesias, María José
Description	Author Affiliation: Fernández Sáez N ( Área de Química Orgánica, Universidad de Almería, Carretera de Sacramento s/n, 04120 Almería, Spain. flortiz@ual.es.)
Abstract	The direct ortho-lithiation of N–H containing (quinolin-8-yl)phosphinimidic amides by reaction with 1 equiv. of n-BuLi described by Wang and co-workers has been re-examined. The multinuclear magnetic resonance $(^{1}H,$ $^{2}H,$ $^{7}Li,$ $^{13}C,$ $^{15}N$ and $^{31}P)$ study of the species formed in the monolithiation of N-(tert-butyl)-P,P-diphenyl-N′-(quinolin-8-yl)phosphinimidic amide 5 with n-BuLi in THF showed that proton abstraction occurred exclusively and quantitatively at the NH. The combination of the NMR results with a DFT study made it possible to describe the structure of the N-lithiated species 9 as a dimer consisting of an eight-membered ring showing two lithium ions triply coordinated to nitrogen atoms corresponding to the deprotonated amine and aminoquinoline moieties of different monomers. The formation of a polymer featuring the same coordination mode couldn't be excluded. In addition, optimized conditions for the efficient derivatization of 5via ortho-lithiation were realised. The reaction of 5 with 2.4 equiv. of t-BuLi in THF in the temperature range of −80 °C to 25 °C for 3 h afforded a $N,C_{ortho}-dilithiated$ species that was trapped with a series of electrophiles leading to new functionalized ortho derivatives of 5 in good yields.
ISSN	14779226
Issue Number	25
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-07-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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