Desymmetrization of Cyclohexa-2,5-dienes through a Diastereoselective Protonation−Hydroamination Cascade

Intramolecular hydroamination of cyclohexa-2,5-dienes led with high selectivity to the corresponding bicyclic allylic amines. This study
demonstrates that the reaction does not proceed through a direct hydroamination of one of the diastereotopic olefins but more likely involves
a diastereoselective protonation of a pentadienyl anion, followed by addition of a lithium amide across the double bond of the resulting
1,3-diene, and is concluded by a highly regioselective protonation of the final allylic anion.