Directing-Group-Free Arene C(sp<sup>2</sup>)–H Amination Using Bulky Aminium Radicals and DFT Analysis of Regioselectivity
Nicole Erin Behnke, Young‐Do Kwon, Michael T. Davenport, Daniel H. Ess, László Kürti
Abstract
A hydroxylamine-derived electrophilic aminating reagent produces a transient and bulky aminium radical intermediate upon in situ activation by either TMSOTf or TFA and a subsequent electron transfer from an iron(II) catalyst. Density functional theory calculations were used to examine the regioselectivity of arene C–H amination reactions on diversely substituted arenes. The calculations suggest a simple charge-controlled regioselectivity model that enables prediction of the major C(sp 2 )–H amination product.
Topics & Concepts
RegioselectivityAminationChemistryHydroxylamineElectrophileReagentElectrophilic aminationDensity functional theoryRadicalMedicinal chemistryCatalysisPhotochemistryOrganic chemistryComputational chemistrySynthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsRadical Photochemical Reactions