Electrophilic intermolecular halo-phosphorothiolation and phosphorothiolation–dearomatization of alkenes/alkynes with N-phosphorothiosuccinimide

Abstract

Electrophilic phosphorothiolations represent an attractive strategy that has been rarely explored due to the lack of practical electrophilic reagents. Herein, we developed electrophilic phosphorothioate transfer reagents and unveiled their synthetic application in the electrophilic intermolecular halo-phosphorothiolation of unactivated alkenes with TMSX as an activator and a nucleophilic halogen source. In addition, phosphorothiolation–dearomatization of alkynes was also achieved to furnish phosphorothiolated spiro[4,5]trienones. Notably, the developed method is successfully employed for the late-stage modification of pharmaceutical molecular derivatives.