Tetramers chiral lithium amides

In summary, chelating chiral lithium amides exist in either of four major structural motifs or mixtures of them (Scheme 3). Non-coordinating solvents generally favor cyclic trimers, A. Ladder tetramers are favored for pyrrolidide amides in the absence of coordinating solvents. 

Aliphatic aldehydes have been butylated enantioselectively using -butyllithium and chiral lithium amides. Mixed lithium amide-Bu Li complexes gave a faster asymmetric reaction, compared with Bu Li in the form of its tetramer. 

The lithium derivative of the chiral chelating diamine (3 )-2-(l-pyrrolidinylmethyl)-pyrrolidine (6) has been used extensively in stereoselective synthesis, i.e. in the deprotonation of ketones and rearrangement of epoxides to homoallylic alcohols. The lithium amide has been crystallized from toluene solution, and X-ray analysis revealed that it forms a ladder-type tetramer with the two pyrrolidine nitrogens solvating the two lithiums at the end of the ladder38, (Li-6)4. 

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