Aminohalogenation of maleimides with alkylamines and XCH₂CH₂X (X = Cl, Br)

Abstract

The nucleophilic substitution of organohalides with alkylamines is one of the most heralded reactions in synthetic chemistry. However, the resulting halide anions are often wasted in routine workup experiments and not fully utilized. Herein, we report a halogen recycling strategy for radical aminohalogenation of maleimides with XCH2CH2X (X = Cl, Br) and alkylamines with excellent functional group compatibility. The strategy's excellent generality is demonstrated by 38 aminohalogenated products, twofold aminochlorination, and late‐stage vinylchlorination of nortriptyline.