Transition metal photoredox catalysis of radical thiol-ene reactions.

We describe the anti-Markovnikov hydrothiolation of olefins using visible-light-absorbing transition metal photocatalysts. The key thiyl radical intermediates are generated upon quenching of photoexcited Ru*(bpz)3(2) with a variety of thiols. The adducts of a wide variety of olefins and thiols are formed in excellent yield (73-99%).

Crossed Intermolecular [2+2] Cycloaddition of Styrenes by Visible Light Photocatalysis.

We report a method for the crossed [2+2] cycloaddition of styrenes using visible light photocatalysis. Few methods for the synthesis of unsymmetrically substituted cyclobutanes by photochemical [2+2] cycloaddition are known. We show that careful tuning of the electrochemical properties of a ruthenium photocatalyst enable the efficient crossed [2+2] cycloaddition of styrenes upon irradiation with visible light.