Quaternary Allylic Amines by Asymmetric Aza-Claisen Rearrangements

Significance

Allylic amines are key intermediates in the synthesis of quaternary amino acids. The authors recently reported a highly active catalyst for the Overman rearrangement of E-configured allylic PMP-trifluoroacetimidates (Angew. Chem. Int. Ed. 2006, 45, 5694). They now extend this methodology to the synthesis of highly enantioenriched quaternary allylic amines. The products can be further derivatized to unsymmetrically α,α-di­substituted or β,β-disubstituted amino acids.