The arylethylamine pharmacophore is conserved across a range of biologically active natural products and pharmaceuticals, particularly in molecules that act on the central nervous system. Herein, we present a photoinduced coppercatalyzed azidoarylation of alkenes at a late stage with arylthianthrenium salts, allowing access to highly functionalized acyclic (hetero)arylethylamine scaffolds that are otherwise difficult to access. A mechanistic study is consistent with a rac-BINAP-Cu I -azide (2) as the photoactive catalytic species. We show the utility of the new method by the expedient synthesis of racemic melphalan in four steps through C−H functionalization.

Herein, we report a photocatalyzed Meerwein‐type bromoarylation of alkenes with stable arylthianthrenium salts, formed by site‐selective C−H thianthrenation. This protocol can be applied to late‐stage functionalization of a variety of biomolecules that are difficult to access by other aryl coupling reagents. Halogen introduction allows for a variety of follow‐up transformations, affording numerous biologically active skeletons.

Herein, we report a photocatalyzed Meerwein‐type bromoarylation of alkenes with stable arylthianthrenium salts, formed by site‐selective C−H thianthrenation. This protocol can be applied to late‐stage functionalization of a variety of biomolecules that are difficult to access by other aryl coupling reagents. Halogen introduction allows for a variety of follow‐up transformations, affording numerous biologically active skeletons.