Allylic Chloro-Tetrahydropyridines: Kinetic Resolutions and Stereospecific Reactions of Enantiomerically Enriched Allyl Chlorides

We report the kinetic resolution of racemic allyl chlorides via a copper-catalysed asymmetric allylic alkylation. Novel 3-alkyl substituted tetrahydropyridines and enantioenriched 3-chloro-1,2,3,6-tetrahydropyridines are formed in high enantioselectivities. The piperidine-based allyl halides undergo highly enantiospecific substitution reactions with C, N, O and S-based nucleophiles. Experiments with deuterium-labelled chloro-tetrahydropyridine and DFT calculations were used to investigate the mechanistic pathways of the reactions.