Recent Discovery on Metal‐Free Construction of S‐Aryl Phosphorothioate Diesters

Recent innovations in metal‐free phosphorothioate synthesis have underscored increased utility as a sustainable alternative to metal‐catalyzed procedures. Green approaches, such as metal‐free coupling reactions and oxidations, radical‐induced methods, electrochemical processes, and multicomponent reactions, were reported from 2020 to 2025 for the successful development of S‐aryl phosphorothioates and S‐heterocyclic phosphorothioates. These methods involve high atom economy, broad functional group tolerance, and mechanistic studies, positioning metal‐free phosphorothiolation as an emergent tool of power and sustainability in modern organic synthesis under a green system.