Asymmetric Cα‐Alkylation of Pipecolic Acid via Curtin‐Hammett Controlled Diastereoselective N‐Alkylation

An efficient asymmetric synthetic approach for the synthesis of C alpha-substituted pipecolic acid has been investigated through utilizing an N-fused bicyclic system. Despite the fluxionality of the pipecolic imidazolidinone, N-alkylation proceeded in high yield with excellent selectivity. The subsequent [2,3]-Stevens rearrangement afforded C alpha-substituted pipecolic acid derivatives successfully. The computational study revealed that the diastereoselectivity during N-alkylation is governed by Curtin-Hammett kinetics.