Iron(iii)-catalyzed direct C–H radical amination of (hetero)arenes

Abstract

Arylamines are regarded as the fundamental structure of many agrochemicals, marketed drugs and organic materials. The development of methods for the efficient and selective construction of these structural motifs from simple building blocks is desirable but still challenging. Herein we have developed an efficient method for the construction of aromatic amines with regioselectivity via the iron-catalyzed intermolecular radical amination of arenes with N-hydroxyphthalimide (NHPI) under air conditions. The key point of this reaction is the formation of the phthalimidyl radical by the homolytic cleavage of the C–N bond of NHPI in the presence of Fe(OTf)₃ and P(OMe)₃. Furthermore, DFT studies on the key transition states was conducted to underly the regioselectivity of this transformation.