{"doi":"10.1126/science.adi9226","title":"Cross-coupling by a noncanonical mechanism involving the addition of aryl halide to Cu(II)","abstract":"Copper complexes are widely used in the synthesis of fine chemicals and materials to catalyze couplings of heteroatom nucleophiles with aryl halides. We show that cross-couplings catalyzed by some of the most active catalysts occur by a mechanism not previously considered. Copper(II) [Cu(II)] complexes of oxalamide ligands catalyze Ullmann coupling to form the C-O bond in aryl ethers by concerted oxidative addition of an aryl halide to Cu(II) to form a high-valent species that is stabilized by radical character on the oxalamide ligand. This mechanism diverges from those involving Cu(I) and Cu(III) intermediates that have been posited for other Ullmann-type couplings. The stability of the Cu(II) state leads to high turnover numbers, >1000 for the coupling of phenoxide with aryl chloride electrophiles, as well as an ability to run the reactions in air.","journal":"Science","year":2023,"id":317768,"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":73,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9563,"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":1024020,"name":"Eva Lin","orcid":"0009-0009-7562-1761","position":1,"is_corresponding":false},{"id":1024021,"name":"Qin-An Huang","orcid":"0000-0002-5185-1097","position":2,"is_corresponding":false},{"id":242487,"name":"Isaac Furay Yu","orcid":"0000-0001-9659-2204","position":3,"is_corresponding":false},{"id":334946,"name":"Guodong Rao","orcid":"0000-0001-8043-3436","position":4,"is_corresponding":false},{"id":334947,"name":"Lizhi Tao","orcid":"0000-0001-9921-2297","position":5,"is_corresponding":false},{"id":1024022,"name":"Ana Jed","orcid":"0009-0005-3210-5581","position":6,"is_corresponding":false},{"id":1024023,"name":"Serena Fantasia","orcid":"0000-0001-6036-6600","position":7,"is_corresponding":false},{"id":848557,"name":"Kurt Püntener","orcid":"0000-0003-1584-0451","position":8,"is_corresponding":false},{"id":334945,"name":"R. David Britt","orcid":"0000-0003-0889-8436","position":9,"is_corresponding":false},{"id":242491,"name":"John F. Hartwig","orcid":"0000-0002-4157-468X","position":10,"is_corresponding":false},{"id":1024019,"name":"Connor P. Delaney","orcid":"0000-0002-6885-6011","position":0,"is_corresponding":true}],"reference_count":53,"raw_metadata":null,"created_at":"2026-07-19T01:06:55.884740Z","pmid":"37676958","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":[]}