A scalable arylation strategy has been developed for the biomass derived synthon cyrene via cross-coupling of halogenated enamines. Stable, halogenated enamines derived from the ketone cyrene were prepared by electrophilic halogenation of the corresponding enamine with either N-iodo- or N-bromosuccinimide. The Suzuki–Miyaura coupling of the iodinated enamine with arylboronic acids followed by acidic hydrolysis afforded α-substituted ketones stereoselectively in isolated yields up to 78%, which was an improvement upon previous routes to these materials. Investigations into the Sonogashira and Mizoroki–Heck coupling of halogenated enamines gave novel electron rich π-systems which may find use as platforms in materials chemistry or further enantioselective synthesis.