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Updated: Apr 26, 2026

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Chiral lithium diamides derived from linked N-isopropyl valinol or alaninol
Chicheung Su1, Jie Guang, Weibin Li
1Department of Chemistry, Brown University , Providence, Rhode Island 02912, United States.
Abstract:
Four different chiral diamino diethers synthesized from N-isopropyl valinol or N-isopropyl alaninol were lithiated with n-butyllithium in tetrahydrofuran or diethyl ether. Crystal structures of the dilithiated diamino diethers were determined by X-ray diffraction. Three dilithiated diamino diethers including (2S,2'S)-1,1'-(butane-1,4-diylbis(oxy))bis(N-isopropylpropan-2-amine) 7, (2S,2'S)-1,1'-(pentane-1,5-diylbis(oxy))bis(N-isopropylpropan-2-amine) 8, and (2S,2'S)-1,1'-(heptane-1,7-diylbis(oxy))bis(N-isopropyl-3-methylbutan-2-amine) 9 are dimers, whereas dilithiated (2S,2'S)-1,1'-(pentane-1,5-diylbis(oxy))bis(N-isopropyl-3-methylbutan-2-amine) 10 is a monomer. The lithium atoms in all crystal structures adopt a nonequivalent coordination protocol and exist in two different environments in which one of the lithium atoms is tetra-coordinated while the other one is tri-coordinated. The solution structures of the dilithiated diamino diethers are also characterized by a variety of NMR experiments including diffusion-ordered NMR spectroscopy (DOSY) with diffusion coefficient-formula (D-FW) weight correlation analyses and other one- and two-dimensional NMR techniques.
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