Photocatalysis enables chemodivergent radical polar crossover : Ritter-type amidation vs Heck-type olefin carbofunctionalizations

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Lepori, Mattia and Pratley, Cassie and Dey, Indrasish and Roider, Veronika and Barham, Joshua Philip (2025) Photocatalysis enables chemodivergent radical polar crossover : Ritter-type amidation vs Heck-type olefin carbofunctionalizations. Other. ChemRxiv. (https://doi.org/10.26434/chemrxiv-2025-cjjxv)

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Abstract

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.

ORCID iDs

Lepori, Mattia, Pratley, Cassie, Dey, Indrasish, Roider, Veronika and Barham, Joshua Philip ORCID logoORCID: https://orcid.org/0000-0003-1675-9399;
CORE (COnnecting REpositories)