A Protocol for the <i>exo</i>-Mono and <i>exo</i>,<i>exo</i>-Bis Functionalization of the Diazocine Ring of Tröger’s Base

An efficient protocol has been developed for the <i>exo-</i>mono and <i>exo</i>,<i>exo</i>-bis functionalization of Tröger’s base in the benzylic 6 and 12 positions of the diazocine ring. The lithiation of Tröger’s base using <i>s</i>-BuLi/TMEDA followed by electrophilic quench affords <i>exo</i>-mono- and <i>exo</i>,<i>exo</i>-bis-substituted derivatives of Tröger’s base in good to excellent yields. The variation of the number of equivalents of <i>s</i>-BuLi/TMEDA and the order of addition of the electrophile strongly govern the outcome of the reaction for each electrophile