Conventional
approaches to Pd-catalyzed alkene 1,2-carboamination
rely upon the combination of a <i>nucleophilic</i> nitrogen-based
component and an internal C-based or external oxidant. In this study,
we outline an umpolung approach, which is triggered by oxidative initiation
at an <i>electrophilic</i> N-based component and employs
“standard” organometallic nucleophiles to introduce
the new carbon-based fragment. Specifically, oxidative addition of
a Pd(0)-catalyst into the N–O bond of <i>O</i>-pentafluorobenzoyl
oxime esters generates imino-Pd(II) intermediates, which undergo 5-<i>exo</i> cyclization with sterically diverse alkenes. The resultant
alkyl-Pd(II) intermediates are intercepted by organometallic nucleophiles
or alcohols, under carbonylative or noncarbonylative conditions, to
provide 1,2-carboamination products. This approach provides, for the
first time, a unified strategy for achieving alkene 1,2-amino-acylation,
-carboxylation, -arylation, -vinylation, and -alkynylation. For carbonylative
processes, orchestrated protodecarboxylation of the pentafluorobenzoate
leaving group underpins reaction efficiency. This process is likely
a key feature in related Narasaka–Heck cyclizations and accounts
for the efficacy of <i>O</i>-pentafluorobenzoyl oxime esters
in aza-Heck reactions of this type