Enantioselective Palladium‐Catalyzed Directed Migratory Allylation of Remote Dienes.

Chain walking has been an efficient route to realize the functionalization of inert C(sp3)−H bonds, but this strategy is limited to mono‐olefin migration and functionalization. Herein, we demonstrate the feasibility of tandem directed simultaneous migrations of remote olefins and stereoselective allylation for the first time. The adoption of palladium hydride catalysis and secondary amine morpholine as solvent is critical for achieving high substrate compatibility and stereochemical control with this method. The protocol is also applicable to the functionalization of three vicinal C(sp3)−H bonds and thus construct three continuous stereocenters along a propylidene moiety via a short synthetic process. Preliminary mechanistic experiments corroborated the design of simultaneous walking of remote dienes. [ABSTRACT FROM AUTHOR]