2D 7Li,15N heteronuclear shift correlation through scalar coupling has successfully been applied to several lithium organyls consisting of polydentate N ligands such as N,N,N′,N′-tetramethylethylenediamine (tmeda), N,N,N′,N′,N′′-pentamethyldiethylentriamine (pmdta) and (−)-sparteine. Structural insights on the conformation of benzyllithium⋅pmdta (5) in a toluene solution and the strength of ion pairing in combination with PGSE NMR measurements, 1H,1H-NOESY and 1H,7Li-HOESY experiments are presented. By studying in detail the formation of 5 in solution, a transient species has been observed for the first time and assigned to a pre-complex of nBuLi and pmdta. In addition, the solution behaviour of the complex formed between benzyllithium and (−)-sparteine (8) has been studied by PGSE and multinuclear NMR spectroscopy. The straightforward synthesis and first applications in asymmetric lithiations are also reported, which show that the new system benzyllithium⋅(−)-sparteine (8) provide poorer enantioselective induction than the classical nBuLi⋅(−)-sparteine (6). The results were supported by deprotonation experiments confirming that the formation of 8 relies on two relevant factors, namely temperature and lithiating reagent. The existence of 8 may thus interfere with the asymmetric induction when the system nBuLi⋅ (−)-sparteine is used in the enantioselective deprotonations of N-Boc-N-(p-methoxyphenyl)-benzylamine conducted in toluene.