{"doi":"10.1021/jacs.3c01662","title":"Benzylic C–H Esterification with Limiting C–H Substrate Enabled by Photochemical Redox Buffering of the Cu Catalyst","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 II to Cu I, 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","year":2023,"id":318290,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":66,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9466,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2023-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1025380,"name":"Chaofeng Zhang","orcid":"0000-0002-1265-8681","position":1,"is_corresponding":false},{"id":246768,"name":"Si-Jie Chen","orcid":"0000-0001-9836-6892","position":2,"is_corresponding":false},{"id":279589,"name":"Aristidis Vasilopoulos","orcid":"0000-0001-7494-7801","position":3,"is_corresponding":false},{"id":251447,"name":"Ilia A. Guzei","orcid":"0000-0003-1976-7386","position":4,"is_corresponding":false},{"id":110277,"name":"Shannon S. Stahl","orcid":"0000-0002-9000-7665","position":5,"is_corresponding":false},{"id":279590,"name":"Dung L. Golden","orcid":"0000-0002-9044-4873","position":0,"is_corresponding":true}],"reference_count":62,"raw_metadata":null,"created_at":"2026-07-19T01:07:01.300821Z","pmid":"37084265","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}