Lepori, Mattia and Pratley, Cassie and Dey, Indrasish and Butera, Valeria and Roider, Veronika and Barham, Joshua P. (2025) Photocatalysis Enables Chemodivergent Radical Polar Crossover: Ritter-Type Amidation vs Heck-Type Olefin Carbofunctionalizations. CHEMISTRY-A EUROPEAN JOURNAL, 31 (33): e202500666. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
Three-component alkene difunctionalization reactions constitute an ideal platform to rapidly build molecular complexity, enabling the simultaneous introduction of two distinct, orthogonal functional groups into the C & boxH;C bond in a single step. Herein, a photoredox catalyzed Ritter-type carboamidation of electronically diverse styrenes harnessing non-stabilized, nucleophilic primary radicals generated from readily-accessible carboxylic acid-derived redox active esters is reported. Furthermore, it is found that Heck-type products are chemoselectively obtained by simply switching aryl olefin acceptors with 1,1-diarylolefins. In the context of photocatalytic chemodivergent radical polar crossover, the synthesis of various trisubstituted alkenes was achieved, simultaneously revealing a divergence in the activation of redox-active esters toward reduction. In-depth mechanistic studies demonstrated both transformation pathways, while DFT calculations indicated the origin of product switchability. Both Ritter-type and Heck-type olefin carbofunctionalizations are scalable up to 4 mmol scale in batch and continuous flow, proving the synthetic utility of the methodology.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | LATE-STAGE FUNCTIONALIZATION; REDOX-ACTIVE ESTERS; PHOTOREDOX; ALKENES; N-(ACYLOXY)PHTHALIMIDES; DIFUNCTIONALIZATION; POTENTIALS; ALKYLATION; AMINO; CARBOAMINATION; chemodivergent; continuous flow; Heck reaction; photoredox catalysis; Ritter carboamidation |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 07 May 2026 04:35 |
| Last Modified: | 07 May 2026 04:35 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66694 |
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