Development of an Anomalous Heck Reaction:  Skeletal Rearrangement of Divinyl and Enyne Carbinols

A general set of conditions that achieves the union of aryl halides and divinyl or enyne carbinols to afford tri- or tetrasubstituted olefins in good yields (up to 83%) is described. The mechanism by which this proceeds is believed to involve the intermediacy of a cyclopropanol, followed by a novel skeletal reorganization. The ability to suppress β-hydride elimination of organopalladium intermediates appears to be critical to the success of these processes.