Palladium‐Mediated Substitution of LGO and Cyrene via Stable Halogenated Enamines

ABSTRACT 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.