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.
Keywords: Alkenes; C–H activation; Distal C–H functionalization; Palladium/norbornene; “exo”-type directing group.