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

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 1521-3765 (https://doi.org/10.1002/chem.202500666)

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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═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.

ORCID iDs

Barham, Joshua P. ORCID: https://orcid.org/0000-0003-1675-9399

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• Item metadata

  Item type:	Article
  ID code:	92966
  Dates:	Date Event 12 June 2025 Published 6 May 2025 Published Online 11 March 2025 Accepted 20 February 2025 Submitted
  Subjects:	Science > Chemistry
  Department:	Faculty of Science > Pure and Applied Chemistry
  Depositing user:	Pure Administrator
  Date deposited:	29 May 2025 15:39
  Last modified:	09 Aug 2026 10:33
  URI:	https://strathprints.strath.ac.uk/id/eprint/92966