Organophotocatalyzed Mono- and Bis-Alkyl/Difluoroalkylative Thio/Selenocyanation of Alkenes.

Organophotocatalyzed three-component 1,2-difluoroacetyl/alkyl/perfluoroalkylative thio/selenocyanation of styrene derivatives under stoichiometric, transition metal-, oxidant-, and additive-free, and mild redox-neutral conditions is reported. Organophotocatalyst 4CzIPN operates the overall radical-polar-crossover mechanistic cycle via initial oxidative luminescence quenching, and the key intermediates were experimentally detected. Selective mono-alkylative thiocyanation of alkenes using dibromoalkanes is also demonstrated. This one-pot synthetic methodology is suitable for primary, secondary, and tertiary alkyl halides and also extended for double alkylative thiocyanation of the dibromoalkanes with excellent yields.