Sequential One-Pot (Het)arene Thioetherification and Amination with Nickel and Visible Light

The development of predictable methods to increase molecular complexity is of paramount importance in modern organic chemistry, especially in the context of synthesizing multifunctionalized (het)arenes in active pharmaceutical ingredients (APIs) and materials. While considerable progress has been made using various protocols, sequential one-pot carbon–heteroatom cross-coupling reactions remain challenging. Herein, we report reaction conditions under adaptive dynamic homogeneous catalysis (AD-HoC) that offer a facile introduction of functional groups onto (het)aromatic scaffolds, resulting in significantly increased molecular complexity and controlled construction of a diverse library of molecules. Moreover, the photoredox reaction conditions employed in AD-HoC introduce a layer of versatility, as the conditions offer distinct selectivity in reactions involving pyrimidines. Manipulating the selectivity is of tremendous value in designing targeted synthesis routes for specific molecules and APIs. The simplicity and predictability of AD-HoC reaction conditions, along with the benefits of photoredox chemistry, make this approach an appealing choice for researchers aiming to create complex molecules.