Enantiomerically Enriched Tetrahydropyridine Allyl Chlorides

Enantiomerically enriched allyl halides are rare due to their configurational lability. Here we report stable piperidine-based allyl chloride enantiomers. These allyl chlorides can be produced via resolution, and undergo highly enantiospecific catalyst-free substitution reactions with C, N, O and S-based nucleophiles. Deuterium-labelled chloro-tetrahydropyridine, selectively prepared using the H/D primary kinetic isotope effect, and DFT calculations were used to investigate the mechanisms of the reactions. The allyl chlorides may also serve as valuable mechanistic tools for probing stereoselective reaction pathways.