Distal Alkenyl C-H Functionalization via the Palladium/Norbornene Cooperative Catalysis

A distal-selective alkenyl C-H arylation method is reported through a directed palladium/norbornene (Pd/NBE) cooperative catalysis. The key is to use an appropriate combination of the directing group and the NBE cocatalyst. A range of acyclic and cyclic cis-olefins are suitable substrates, and the reaction is operated under air with excellent site-selectivity. Preliminary mechanistic studies are consistent with the proposed Pd/NBE-catalyzed C-H activation instead of the Heck pathway. Initial success on distal alkylation has also been achieved using MeI and methyl bromoacetate as electrophiles.