Abstract A mild, redox neutral photocatalytic method for alkene hydrothiolation is reported. Utilizing visible-light activation, catalytic radical initiation is achieved with the transition metal complex Ru (bpy) 3 Cl 2, enabling rapid access to a diverse set of thiol–ene coupled products in excellent yield. On the basis of a strong observed background reaction in some cases, we have developed a solvent-free, Lewis acid-promoted tandem amidation– ...