Dichotomous mechanistic behavior in Narasaka–Heck cyclizations: electron rich Pd-catalysts generate iminyl radicals

Pd-catalyzed cyclizations of oxime esters with pendant alkenes are subject to an unusual ligand controlled mechanistic divergence. Pd-systems modified with electron deficient phosphines (e.g. P(3,5-(CF(3))(2)C(6)H(3))(3)) promote efficient aza-Heck cyclization, wherein C–N bond formation occurs via alkene imino-palladation. Conversely, electron rich ligands, such as P(t-Bu)(3), cause deviation to a SET pathway and, in these cases, C–N bond formation occurs via cyclization of an iminyl radical. A series of mechanistic experiments differentiate the two pathways and the scope of the hybrid organometallic radical cyclization is outlined. This study represents a rare example in Pd-catalysis where selection between dichotomous mechanistic manifolds is facilitated solely by choice of phosphine ligand.