Pd-Catalyzed Allylic Substitution of Azo-Ene Adducts Enables Net Allylic C–H Alkylation of Allylic Alcohols

We present a protocol for a regioselective allylic C–H alkylation of allylic alcohols, consisting of a sequential azo-ene reaction and attendant Pd-catalyzed allylic substitution with Grignard reagents. Notable features of this work include: (1) regioselective C(sp³)–C(sp³) bond formation is achieved under Pd-catalysis, and (2) the allylic substitution proceeds with retention of configuration at the electrophilic allylic carbon as well as the olefin geometry.