Net δ-C−H Alkylation of Allyl Alcohols by Ni-Catalyzed Allylic Substitution of Azo-Ene Adducts

Transformation of allylic C–H bonds into C–C bonds in a regioselective manner represents a powerful approach to generate complex molecules from simple starting materials. Herein, we report a protocol for net δ-C−H alkylation of allyl alcohols involving a sequential azo-ene reaction and attendant Ni-catalyzed allylic substitution with Grignard reagents. This two-step strategy enables the regioselective alkylation of distal C–H bonds, a transformation that remains challenging via direct ap-proaches under transition metal catalysis.