Recent Advances in the Direct Synthesis of Sulfur‐Containing Organophosphorus Compounds via Radical Processes

Abstract Phosphonothioates, phosphinothioates and phosphorothioates are regarded as an important class of sulfur‐containing organophosphorus compounds. Because of the unique P(O)S−R group, these compounds have important biological activities and thus have been widely used in the fields of pharmaceuticals and pesticides. In recent years, the development of sulfur‐containing organophosphorus compounds by radical processes has attracted considerable attention in organophosphorus chemistry. Along these lines, in this review, the recent advances in the synthesis of sulfur‐containing organophosphorus compounds were systematically summarized. According to the different ways of generating radicals during the formation process of phosphonothioates, phosphinothioates and phosphorothioates, these transformations can be divided into four categories: (1) Oxidant or metal‐free promoted radical transformation to fabricate sulfur‐containing organophosphorus compounds; (2) Copper‐catalyzed radical transformation to produce sulfur‐containing organophosphorus compounds; (3) Photo‐induced radical transformation to prepare sulfur‐containing organophosphorus compounds; (4) Electro‐induced radical transformation to derive sulfur‐containing organophosphorus compounds.