Palladium/norbornene-catalyzed distal alkenyl C-H arylation and alkylation of cis-olefins.

In this full article, a detailed study of a distal alkenyl C-H arylation and alkylation through the palladium/norbornene (NBE) cooperative catalysis is described. Both aminopyridine- and oxime ether-type directing groups have been found effective for this transformation, allowing functionalization of diverse allyl amines and homoallyl alcohols. In addition, the C5,C6-substititued NBEs show optimal reactivity and selectivity. Various cis-olefins can be transformed to the corresponding arylated or alkylated trisubstituted alkenes with excellent regio- and stereoselectivity. Preliminary mechanistic studies support the Catellani pathway instead of the Heck pathway.