{"doi":"10.1021/jacs.4c06243","title":"Dioxygenase Chemistry in Nucleophilic Aldehyde Deformylations Utilizing Dicopper O<sub>2</sub>-Derived Peroxide Complexes","abstract":"The chemistry of copper-dioxygen complexes is relevant to copper enzymes in biology as well as in (ligand)Cu–O 2 (or Cu 2 –O 2 ) species utilized in oxidative transformations. For overall energy considerations, as applicable in chemical synthesis, it is beneficial to have an appropriate atom economy; both O-atoms of O 2(g) are transferred to the product(s). However, examples of such dioxygenase-type chemistry are extremely rare or not well documented. Herein, we report on nucleophilic oxidative aldehyde deformylation reactivity by the peroxo-dicopper(II) species [Cu 2 II (BPMPO – )(O 2 2– )] 1+ {BPMPO-H = 2,6-bis{[(bis(2-pyridylmethyl)amino]methyl}-4-methylphenol)} and [Cu 2 II (XYLO – )(O 2 2– )] 1+ (XYLO – = a BPMPO – analogue possessing bis(2-{2-pyridyl}ethyl)amine chelating arms). Their dicopper(I) precursors are dioxygenase catalysts. The O 2(g) -derived peroxo-dicopper(II) intermediates react rapidly with aldehydes like 2-phenylpropionaldehyde (2-PPA) and cyclohexanecarboxaldehyde (CCA) in 2-methyltetrahydrofuran at −90 °C. Warming to room temperature (RT) followed by workup results in good yields of formate (HC(O)O – ) along with ketones (acetophenone or cyclohexanone). Mechanistic investigation shows that [Cu 2 II (BPMPO – )(O 2 2– )] 1+ species initially reacts reversibly with the aldehydes to form detectable dicopper(II) peroxyhemiacetal intermediates, for which optical titrations provide the K eq (at −90 °C) of 73.6 × 10 2 M –1 (2-PPA) and 10.4 × 10 2 M –1 (CCA). In the reaction of [Cu 2 II (XYLO – )(O 2 2– )] 1+ with 2-PPA, product complexes characterized by single-crystal X-ray crystallography are the anticipated dicopper(I) complex, [Cu 2 I (XYLO – )] 1+ plus a mixed-valent Cu(I)Cu(II)-formate species. Formate was further identified and confirmed by 1 H NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS) analysis. Using 18 O 2(g) -isotope labeling the reaction produced a high yield of 18-O incorporated acetophenone as well as formate. The overall results signify that true dioxygenase reactions have occurred, supported by a thorough mechanistic investigation.","journal":"Journal of the American Chemical Society","year":2024,"id":437125,"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":11,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9576,"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":1087507,"name":"Sanjib Panda","orcid":"0000-0001-6556-8009","position":1,"is_corresponding":false},{"id":1087508,"name":"Hai Phan","orcid":"0009-0004-9233-5496","position":2,"is_corresponding":false},{"id":981287,"name":"Bohee Kim","orcid":"0000-0002-0554-3392","position":3,"is_corresponding":false},{"id":414296,"name":"Maxime A. Siegler","orcid":"0000-0003-4165-7810","position":4,"is_corresponding":false},{"id":414300,"name":"Kenneth D. Karlin","orcid":"0000-0002-5675-7040","position":5,"is_corresponding":false},{"id":981286,"name":"Pradip Kumar Hota","orcid":"0000-0002-1502-4879","position":0,"is_corresponding":true}],"reference_count":174,"raw_metadata":null,"created_at":"2026-07-19T02:00:29.872940Z","pmid":"39141923","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":[]}