Iron(II)-Catalyzed Intermolecular Amino-Oxygenation of Olefins through the N–O Bond Cleavage of Functionalized Hydroxylamines

An
iron-catalyzed diastereoselective intermolecular olefin
amino-oxygenation reaction is reported, which proceeds via
an iron-nitrenoid generated by the N–O bond cleavage of a functionalized
hydroxylamine. In this reaction, a bench-stable hydroxylamine derivative
is used as the amination reagent and oxidant. This method tolerates
a range of synthetically valuable substrates that have been all incompatible
with existing amino-oxygenation methods. It can also provide amino
alcohol derivatives with regio- and stereochemical arrays complementary
to known amino-oxygenation methods.