{"doi":"10.1021/acs.joc.4c01062","title":"Investigating Arylazoformamide Ligands in Palladium(II) Precatalysts through the Suzuki–Miyaura Cross-Coupling Reaction","abstract":"Herein, is the reported synthesis and utilization of redox-active arylazoformamide (AAF) ligands in palladium(II) precatalysts for the Suzuki–Miyaura cross-coupling reaction. Complexes were formed from 2 equiv of an AAF ligand with Pd(II)Cl 2 in an appropriate solvent to create the square planar (AAF) 2 PdCl 2 precatalyst. A thorough investigation of aryl bromides and arylboronic acids found that 1.0 mol % precatalyst with cesium carbonate (Cs 2 CO 3 ) as base, 1,4-dioxane as solvent at 90 °C for 24 h allowed for excellent conversions to the biphenyl products (over 20 examples). To highlight the AAF ligand class, a set of comparison reactions were performed with redox-active arylazothioformamide ligands, i.e., an (ATF) 2 PdCl 2 complex, other commercial palladium(II) complexes, and a Ni(II)Cl 2 arylazoformamide coordination complex 2 . The (AAF) 2 PdCl 2 complexes outperformed all of others tested. Mechanistically, it is proposed that the AAF ligand singly reduces to antiferromagnetically couple to the palladium(I) complex as a transmetalation intermediate. Ni-based precatalysts were found to be inactive for the studied Suzuki–Miyaura reaction. Overall, these ligand systems offer a unique look into redox-active palladium cross-coupling reactions as well as being phosphine-free and high yielding.","journal":"The Journal of Organic Chemistry","year":2024,"id":458911,"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":5,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9439,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2024-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":519570,"name":"Elliott B. Hulley","orcid":"0000-0002-2630-3689","position":1,"is_corresponding":false},{"id":435415,"name":"Kristopher V. Waynant","orcid":"0000-0002-4096-5726","position":2,"is_corresponding":false},{"id":1097628,"name":"Laxmi Tiwari","orcid":"0009-0004-6103-4471","position":0,"is_corresponding":true}],"reference_count":45,"raw_metadata":null,"created_at":"2026-07-19T02:03:50.608887Z","pmid":"39630927","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":[]}