Abstract
Aryl dialkyl amines, valuable subunits of a wide range of effect chemicals, are accessed by intramolecular amination of aromatic C-H bonds employing UV photolysis of N-chloroamines. The reactions show good functional group tolerance and allow access to a range of fused and bridged polycyclic structures. The homogeneous reaction conditions allow for the one-pot conversion of secondary amines to their arylated derivatives. Experimental and theoretical evidence supports the involvement of electrophilic aminium radicals which react via direct ortho-attack on the arene.
Highlights
Aromatic amines are fundamental components of a broad range of effect molecules including dyes, pharmaceuticals and agrochemicals.[1]
There remains a signi cant need for a general direct amination of aromatic C–H bonds with simple alkylamine precursors
Outstanding progress has recently been made in this regard (Scheme 1, panel b): Leonori has demonstrated the amination of a range of mono- and bicyclic aromatics with secondary aminium radicals generated by photoredox-mediated homolysis of (2,4-dinitrophenyloxy) amines,[16] while Nicewicz has demonstrated the intermolecular amination of electron-rich arenes with aminium radicals, generated directly from primary amines using acridinium photoredox catalysis coupled with aerobic oxidation.[17]
Summary
Aromatic amines are fundamental components of a broad range of effect molecules including dyes, pharmaceuticals and agrochemicals.[1]. Scheme 1 Direct radical C–H amination of arenes. Edge Article aryloxyamine radical precursors employed successfully by Leonori require multi-step synthesis from secondary amines, while the direct functionalization reported by Nicewicz is far limited to primary amines.
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