Abstract
Dithiane anions undergo intramolecular conjugate additions with α,β-unsaturated nitriles when a dithiane anion is tethered to N-1 of the 3-cyano-1,4,5,6-tetrahydropyridine nucleus. 3-Cyano-1-[2-(1,3-dithianyl-2-yl)ethyl]-1,4,5,6-tetrahydropyridine (1a) and the one-carbon homologue 1b cyclize in the presence of 12-crown-4 to generate indolizidine 3 and quinolizidine 9, in which the nitrile group exhibits a strong, thermodynamic preference for the axial orientation. Oxidation of 1b provides dithiane S-oxide 10 that undergoes a highly stereoselective conjugate addition to provide crystalline quinolizidine 13. The X-ray structure of 13 is reported and corroborates our “peg-in-a-pocket” principle for stereoselective conjugate additions with α,β-unsaturated nitriles.
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