Asymmetric alpha-alkynylation of piperidine via N-sulfinyliminium salts.

Piperidine was stereoselectively alpha-alkynylated in a four-step sequence made up of transformation to a chiral nonracemic N-sulfinylpiperidine, anodic oxidation to N-sulfinyliminium ion equivalent, alkynylation through addition of a mixed organoaluminum derivative, and final acidic deprotection of the sulfoxide. Overall yields are around 50%, and the diastereoselectivity of the nucleophilc addition was between 92 and 99% de, allowing isolation of the final product with 99% enantiomeric purity.