Iron‐Catalyzed Oxidative Hydroxyamination of Alkenes of Unsaturated Keto Oximes with TBHP as the Hydroxy Source

A new iron‐catalyzed hydroxyamination of alkenyl ketoximes using TBHP as the hydroxy source to selectively assemble cyclic nitrones is described. Using inexpensive FeCl3 as the catalyst and TBHP as both the oxidant and hydroxy source, this reaction enables the formation of two new bonds, one C−N bond and one C−O bond, in a single reaction initiating from the oxime side through the nitrogen‐center radical geneation, radical addition across the C=C bond and radical hydroxylation cascades. This reaction has advantages of exquisite selectvity and excellent functional group tolerance, thus providing an economical and efficient strategy for the construction of complex heterocyclic compounds. Iron‐catalyzed oxidative hydroxyamination of alkenes of unsaturated keto oximes with TBHP as the hydroxy source for accessing cyclic nitrones is disclosed. The reaction features excellent selectivity and high functional group tolerance, and represents an economical and efficient one‐step synthesis strategy for the construction of complex heterocyclic compounds.