The N-Boc-protected (S)-prolinamine reacts readily with formaldehyde and diverse alpha-hydroxyimino ketones to give imidazole N-oxides with an enantiomerically pure N-protected (pyrrolidin-2-yl)methyl substituent. Subsequent deprotection yields the corresponding NH derivatives. Upon treatment of these products with Ac2O at room temperature, a cascade of reactions leads to optically active tricyclic products. In all these processes, the stereogenic center is preserved. In one case, the bis-heterocyclic imidazole N-oxide was transformed into the corresponding optically active imidazole-2-thione via a sulfur-transfer reaction with 2,2,4,4-tetramethylcyclobutane-1,3-dithione.