TMSCl-promoted allylic phosphorothiolation and intermolecular difunctionalization of alkenes

Herein, we describe a TMSCl-promoted, divergent strategy for the synthesis of structurally diverse <i>S</i>-alkyl phosphorothioates from various classes of olefins using <i>N</i>-phosphorothiosuccinimide as the phosphorothiolation reagent. For aromatic trisubstituted and 1,1-disubstituted olefins, the reaction proceeds <i>via</i> regioselective allylic phosphorothiolation. In the case of aliphatic 1,1-disubstituted olefins, an electrophilic intermolecular phosphorothiolation-difunctionalization is achieved. Interestingly, with (1-cyclopropylvinyl)benzene, a 1,5-chlorophosphorothiolation product is obtained <i>via</i> allylic ring-opening reaction. This operationally simple and scalable method enables direct transfer of the -SP(O)(OR)₂ moiety and offers opportunities for further synthetic elaboration.