{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Golden DL"],"funding":["National Institute of General Medical Sciences","NIH HHS","NIGMS NIH HHS"],"pagination":["9434-9440"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10510071"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["145(17)"],"pubmed_abstract":["Copper-catalyzed radical-relay reactions provide a versatile strategy for selective C-H functionalization; however, reactions with peroxide-based oxidants often require excess C-H substrate. Here, we report a photochemical strategy to overcome this limitation by using a Cu/2,2'-biquinoline catalyst that supports benzylic C-H esterification with limiting C-H substrate. Mechanistic studies indicate that blue-light irradiation promotes carboxylate-to-copper charge transfer, reducing resting-state Cu<sup>II</sup> to Cu<sup>I</sup>, which activates the peroxide to generate an alkoxyl radical hydrogen-atom-transfer species. This \"photochemical redox buffering\" introduces a unique strategy to sustain the activity of Cu catalysts in radical-relay reactions."],"journal":["Journal of the American Chemical Society"],"pubmed_title":["Benzylic C-H Esterification with Limiting C-H Substrate Enabled by Photochemical Redox Buffering of the Cu Catalyst."],"pmcid":["PMC10510071"],"funding_grant_id":["R35 GM134929","S10 OD020022"],"pubmed_authors":["Vasilopoulos A","Chen SJ","Guzei IA","Stahl SS","Golden DL","Zhang C"],"additional_accession":[]},"is_claimable":false,"name":"Benzylic C-H Esterification with Limiting C-H Substrate Enabled by Photochemical Redox Buffering of the Cu Catalyst.","description":"Copper-catalyzed radical-relay reactions provide a versatile strategy for selective C-H functionalization; however, reactions with peroxide-based oxidants often require excess C-H substrate. Here, we report a photochemical strategy to overcome this limitation by using a Cu/2,2'-biquinoline catalyst that supports benzylic C-H esterification with limiting C-H substrate. Mechanistic studies indicate that blue-light irradiation promotes carboxylate-to-copper charge transfer, reducing resting-state Cu<sup>II</sup> to Cu<sup>I</sup>, which activates the peroxide to generate an alkoxyl radical hydrogen-atom-transfer species. This \"photochemical redox buffering\" introduces a unique strategy to sustain the activity of Cu catalysts in radical-relay reactions.","dates":{"release":"2023-01-01T00:00:00Z","publication":"2023 May","modification":"2025-04-26T04:49:56.33Z","creation":"2025-04-06T11:13:52.498Z"},"accession":"S-EPMC10510071","cross_references":{"pubmed":["37084265"],"doi":["10.1021/jacs.3c01662"]}}