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.