Evaluation and Development of Methodologies for the Synthesis of Thiophosphinic Acids

Thiophosphorus acids R¹R²P(S)OH constitute an important class of organophosphorus compounds, in which the phosphorus atom is intrinsically chiral if R¹ ≠ R². In connection with a project aimed at the preparation of chiral thiophosphorus acids, various available literature methods were considered, but few fit the requirement of odorless reagents. Herein, the results of our studies on the synthesis of thiophosphinic acids are reported. Ultimately, two major approaches were selected: (1) the Stec reaction of phosphorus amides with carbon disulfide; and (2) the one-pot synthesis of thiophosphorus acids from H-phosphinates, an organometallic nucleophile, and quenching with elemental sulfur. An application to the preparation of a potential chiral phosphorus organocatalyst is also reported.