Phosphorothiosulfonates: new radical phosphorothiolation reagents for photocatalytic cyclization of alkenes/alkynes

Abstract

The direct radical phosphorothiolation of alkenes/alkynes has been severely limited by the lack of practical and efficient radical phosphorothiolation reagents. Herein, we report the first synthesis of phosphorothiosulfonates as competent radical –S–P(O)(OR)₂ precursors. Under mild photoredox conditions, these reagents enable metal-free and oxidant-free phosphorothiolation/cyclization of diverse alkenes and alkynes, affording a broad range of phosphorothiolated N-heterocycles and carbocycles in good yields. This strategy offers a straightforward and general platform for the rapid installation of –S–P(O)(OR)₂ groups, significantly expanding the chemical space for radical phosphorothiolation chemistry.