Regio- and Chemoselective Double Allylic Substitution of Alkenyl vic-Diols

Double allylic substitution is an attractive approach to build molecular complexity from simple starting materials by creating two new bonds in one-pot. However, this type of reaction has been doomed by chemoselectivity and regioselectivity issues. In this manuscript, we describe a new approach to introduce a-la-carte two new C–C, C–N, C–O or C–S bonds in a chemo- and regioselective fashion. The reaction relies on sequential dual catalysis with Lewis acid and palladium. The scope is remarkably broad, and the reaction can be diastereoselective using secondary alcohols as the first nucleophile.