Photocatalyzed site-selective aryl C–H sulfinamidation via thianthracene salts

ABSTRACT Benzenesulfinamides are a critical class of S(IV) compounds that serve as important entry points to an array of emerging pharmaceutical molecules and bioactive substances. However, the widespread application is limited by immature synthetic methods, typically requiring pre-functionalized aryl halides or organometallic reagents, and harsh reaction conditions. Herein, we report an environmentally benign photocatalyzed metal-free approach which enables the C(sp 2 )−S coupling between aryl thianthracene (TT) salts and N -sulfinylamines, and can make thianthracene a traceless and recyclable leaving group through single electron transfer (SET) reduction. This simple modular method proceeds under mild conditions with high functional group tolerance, and the modification of complex aromatic core structures and pharmaceutical derivatives further validates its practical value.