Synthetic Studies in the Intramolecular Carbocyclization of <i>N</i>-Acyloxyiminium Ions. Stereoelectronic and Steric Implications of Nucleophilic Alkene, Alkyne, and Allene Tethers

N-Acyloxyiminium ions generated from 4-substituted l-pyroglutamic esters with 4-(3-butenyl), 4-(3-butynyl), 4-(3-cinnamylmethyl), and 4-allenic tethers undergo rapid Lewis acid mediated carbocyclization to give stereodefined azacyclic compounds depending on the nature of the nucleophilic tether. In general, reactions of alkenes and alkynes with terminal alkyl or aryl substituents, as well as allenes, proceed through transient vinylic carbocations that are attacked internally by the N-Boc group to give tricyclic dihydrooxazinones. Diastereotopic bis-4-(3-butenyl) and 4-(3-butynyl) tethers undergo stereochemically controlled attack favoring an antiperiplanar rather than synclinal approach to give enantiopure 6-halo octahydroindole-2-carboxylic acids and 6-halo hexahydroindole-2-carboxylic acids as their methyl esters, respectively. The aza bicyclic and tricyclic compounds are excellent scaffolds for diversification.