Radical aryl migrations are powerful techniques to forge new bonds in aromatic compounds. The growing popularity of photoredox catalysis has led to an influx of novel strategies to initiate and control aryl migration starting from widely available radical precursors. This review encapsulates progress in radical aryl migration enabled by photochemical methodsparticularly photoredox catalysissince 2015. Special attention is paid to descriptions of scope, mechanism, and synthetic applications of each method.

Arene dearomatization reactions are an important class of synthetic technologies for the rapid assembly of unique chemical architectures. Herein, we report a catalytic protocol to initiate a carboamination/dearomatization cascade that proceeds through transient sulfonamidyl radical intermediates formed from native sulfonamide N-H bonds leading to 1,4cyclohexadiene-fused sultams. Importantly, this work demonstrates a facile approach to employ two-dimensional aromatic compounds as modular building blocks to generate richly substituted, three-dimensional compounds. These reactions occur at room temperature under visible light irradiation and are catalyzed by the combination of an iridium(III) photocatalyst and a dialkyl phosphate base. Reaction optimization, substrate scope, mechanistic features, and synthetic applications of this transformation are presented.

Arylethylamines are abundant motifs in myriad natural products and pharmaceuticals, so efficient methods to synthesize them are valuable in drug discovery. In this work, we disclose an intramolecular alkene aminoarylation...

We disclose an intermolecular 1,2-aminoarylation of alkenes using aryl sulfinamide reagents as bifunctional amine and arene donors. This reaction features excellent regio- and diastereoselectivity on a variety of activated and unactivated substrates. Using a weakly oxidizing photoredox catalyst, a sulfinamidyl radical is generated under mild conditions and adds to an alkene to form a new C–N bond. A desulfinylative Smiles-Truce rearrangement follows to form a new C–C bond. In this manner, biologically active arylethylamines and valuable building blocks can be rapidly assembled from abundant alkene feedstocks. Additionally, we demonstrate that chiral information from the sulfinamide can be transferred via rearrangement to a new carbon stereocenter in the product, thus advancing development of traceless asymmetric alkene difunctionalization methodologies.

Arylethylamines are abundant motifs in myriad natural products and pharmaceuticals, so efficient methods to synthesize them are valuable in drug discovery. In this work, we disclose an intramolecular alkene aminoarylation cascade that exploits the electrophilicity of a nitrogen-centered radical to form a C–N bond, then repurposes the nitrogen atom’s sulfonyl activating group as a traceless linker to form a subsequent C–C bond. This photoredox catalysis protocol enables the preparation of densely substituted arylethylamines from commercially abundant aryl sulfonamides under mild conditions. Reaction optimization, scope, mechanism, and synthetic applications are discussed.