Synthesis and Structure of Alkali‐Metal Naphthylamides Solvated by Biorenewable 2‐Methyltetrahydrofuran

Advancing the synthetic and constitutional knowledge of alkali‐metal amides, here we report the synthesis and structural authentication of a family of alkali‐metal N ‐phenyl‐1‐naphthylamides ( 1Li , 1Na , and 1K ) obtained from the deprotonation of the parent amine by an alkali‐metal alkyl base in hexane and using biorenewable 2‐methyltetrahydrofuran (2‐MeTHF) as a Lewis donor. The aggregation and degree of donor‐solvation of these complexes differ depending on the nature of the alkali‐metal. Furthermore, the lithium N ‐phenyl‐1‐naphthylamide complex 1Li can undergo further metalation on the peri position of the naphthyl ring using either n BuLi or n BuNa as a base to give complexes 2LiLi , and 2LiNa , respectively. X‐ray crystallographic studies established the molecular structures of these complexes in which both alkali‐metals are chelated by a novel C , N ‐dianionic bidentate ligand. Quenching of 2LiLi , and 2LiNa with D 2 O provided further evidence supporting that the NH, C( peri )‐H di‐metalation has occurred.