Probing the Origins of Asymmetric Induction by 3-Aminopyrrolidine Lithium Amides Complexes:  A ⁶Li/¹H/¹³C NMR Study

The structure of two chiral N, N ‘-disubstituted-3-aminopyrrolidine lithium amides 3 and 4 in solution in THF- d 8 has been studied at low temperatures by high-field 1 H, 13 C, and 6 Li NMR spectroscopy. Despite their structural analogy, these two compounds adopt very different conformations in solution: while the amide 3 pyrrolidinic ring undergoes only minor changes with respect to its amino precursor 1, amide 4 presents a norbornyl-like bridged structure around 6 Li + . When excess Bu 6 Li is added to both amide solutions, 1:1 amide−Bu 6 Li complexes arise, and their structures appear, this time, very similar and organized around a parallepipedic N−Li 2 −C core, the two lithium cations bridging the amide and the alkyl chain. The 4 −Bu 6 Li complex appears very tight, with two distinct signals corresponding to each of the diastereotopic α-protons of butyllithium, by contrast with the looser 3 −Bu 6 Li complex. From all these data, we propose a model to interpret the results obtained using these chiral amides in the asymmetric condensation of butyllithium with aromatic aldehydes.