Catalyst‐ and Light‐free S−H Insertion between Phosphorodithioic Acids and Diazo Compounds: Rapid Access to Dialkylphosphorodithioates

Abstract A catalyst‐ and light‐free S−H insertion of phosphorodithioic acids with diazo compounds has been developed, in which phosphorodithioic acid acts not only as an acid promoter but also as a nucleophile. This protocol features fast reaction rate, broad substrate scope, mild conditions, and simple operation, providing a cost‐effective and general approach to diverse phosphorodithioates.