Cation--interaction-facilitated, self-photocatalyzed and regioselective perfluoroalkylation of 3-aza-1,5-dienes

A self-photocatalyzed perfluoroalkylation/cyclization cascade of 3-aza-1,5-dienes enabled by an unprecedented cation-& pi;-interaction is presented. The reaction proceeds with a great regioselectivity to provide 3-perfluoroalkyl4-pyrrolin-2-ones under exogenous-photocatalyst-, transition-metal- and organoamine-free conditions, with Cs2CO3 playing dual roles as both a photoactivator and a base. It is readily scalable to a 2-gram scale, and could be induced by the natural sunlight.