An umpolung approach to acyclic 1,4-dicarbonyl amides via photoredox-generated carbamoyl radicals

Williams, Jason D. and Leach, Stuart G. and Kerr, William J. (2023) An umpolung approach to acyclic 1,4-dicarbonyl amides via photoredox-generated carbamoyl radicals. Chemistry - A European Journal, 29 (28). e202300403. ISSN 1521-3765 (https://doi.org/10.1002/chem.202300403)

[thumbnail of Williams-CEJ-2023-An-umpolung-approach-to-acyclic-1-4-dicarbonyl-amides-via-photoredox]
Preview
 Text. Filename: Williams_CEJ_2023_An_umpolung_approach_to_acyclic_1_4_dicarbonyl_amides_via_photoredox.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (6MB)| Preview

Abstract

A method for the generation and reaction of carbamoyl radicals from oxamate salts, followed by reaction with electron-poor olefins, is described. The oxamate salt acts as a reductive quencher in the photoredox catalytic cycle, allowing mild and mass-efficient formation of 1,4-dicarbonyl products; a challenging transformation in the context of functionalized amide formation. Increased understanding has been obtained by the use of ab initio calculations, in support of experimental observations. Furthermore, steps have been taken towards an environmentally-friendly protocol, by utilizing sodium as a cheap and low mass counterion, and demonstrating successful reactions using a metal-free photocatalyst and a sustainable, non-toxic solvent system.

ORCID iDs

Williams, Jason D. ORCID logoORCID: https://orcid.org/0000-0002-4742-6848, Leach, Stuart G. and Kerr, William J. ORCID logoORCID: https://orcid.org/0000-0002-1332-785X;
CORE (COnnecting REpositories)