{"doi":"10.1002/chem.202303428","title":"Intramolecular Carboxyamidation of Alkyne‐Tethered <i>O</i>‐Acylhydroxamates through Formation of Fe(III)‐Nitrenoids","abstract":"We developed intramolecular carboxyamidations of alkyne-tethered O-acylhydroxamates followed by either thermally induced spontaneous or 4-(dimethylamino)pyridine-catalyzed O→O or O→N acyl group migration. Under iron-catalyzed conditions, the carboxyamidation products were generated in high yield from both Z-alkene and arene-tethered substrates. DFT calculations indicate that the iron-catalyzed carboxyamidation proceeds via a stepwise mechanism involving iron-imidyl radical cyclization followed by intramolecular acyloxy transfer from the iron center to the alkenyl radical center to furnish the cis-carboxyamidation product. Upon treatment with 4-(dimethylamino)pyridine, the Z-alkene-tethered carboxyamidation products underwent selective O→O acyl migration to generate 2-acyloxy-5-acyl pyrroles. Thermal O→N acyl migration occurs during carboxyamidation if the Z-alkene linker contains an alkyl or an aryl substituent at the β-position of the carbonyl group. On the other hand, the arene linker-containing compounds selectively undergo O→N acyl migration to generate N-acyl-3-acylisoindolinones, and the corresponding O→O acyl migration forming isoindole derivatives was not observed.","journal":"Chemistry - A European Journal","year":2023,"id":371890,"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":6,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9519,"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":518096,"name":"Yu Zhang","orcid":"0000-0001-9412-0246","position":1,"is_corresponding":false},{"id":285942,"name":"Peng Liu","orcid":"0000-0002-8188-632X","position":2,"is_corresponding":false},{"id":669523,"name":"Donald J. Wink","orcid":"0000-0002-2475-2392","position":3,"is_corresponding":false},{"id":669524,"name":"Daesung Lee","orcid":"0000-0003-3958-5475","position":4,"is_corresponding":false},{"id":669522,"name":"Siyuan Su","orcid":"0009-0004-4488-5151","position":0,"is_corresponding":true}],"reference_count":116,"raw_metadata":null,"created_at":"2026-07-19T01:15:49.453761Z","pmid":"38050744","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":[]}