Cesium carbonate-catalyzed synthesis of phosphorothioates via S-phosphination of thioketones

A highly efficient and environmentally-friendly base-mediated transition metal-free direct thiophilic catalytic approach is reported for the synthesis of S-benzhydryl-phosphorothioates by reacting phosphite nucleophiles with diarylmethanethione. A wide variety of thioketones were coupled with different phosphite derivatives to provide the corresponding phosphorothioates in good to excellent yields. The control experiments and density functional theory (DFT) calculations rely on the regio-selective thiophilic addition of a phosphite nucleophile via umpolung protocols.

Automated summary

A highly efficient and environmentally-friendly catalytic method for the synthesis of S-benzhydryl-phosphorothioates has been reported. This method involves the direct thiophilic addition reaction of phosphite nucleophiles with diarylmethanethione, without the need for transition metal catalysts. The reaction yields the corresponding phosphorothioates in good to excellent yields, with a wide variety of thioketones and phosphite derivatives.