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 generating 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 an 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 approaches under transition-metal catalysis.