Aerial dioxygen activation vs. thiol-ene click reaction within a system

Markovnikov or anti-Markovnikov selective thiol-ene click (TEC) reactions and the synthesis of -hydroxysulfides via aerial dioxygen activation are prevalent C-S bond forming reactions of styrenes and thiophenols. Herein, by choosing appropriate environments using solvents with additives or neat conditions, any one of these three reactions was achieved exclusively in excellent yields.