Photocatalysis Enables Chemodivergent Radical Polar Crossover: Ritter-Type Amidation vs Heck-Type Olefin Carbofunctionalizations

Enhancing the sp³-hybridized character of molecular scaffolds (the "Escape from Flatland" strategy) is a crucial target to in-crease the probability of finding new drugs or agrochemicals. In this regard, an ideal platform is provided by three-component alkene difunctionalization reactions, which enable the simultaneous introduction of two distinct, orthogonal functional groups into the C=C bond in a single step. Herein, we report a photoredox catalyzed Ritter-type carboamidation of electronically di-verse styrenes harnessing non-stabilized, nucleophilic primary radicals generated from readily-accessible carboxylic acid-derived redox active esters. Furthermore, it was found that Heck-type products were chemoselectively obtained by simply switching aryl olefin acceptors with 1,1-diarylolefins. In the context of photocatalytic chemodivergence, various trisubstituted alkenes were synthesized. Both Ritter-Type and Heck-type olefin carbofunctionalizations were scalable up to 4 mmol scale in batch and continuous flow.