{"doi":"10.1021/jacs.3c03982","title":"BF <sub>3</sub> -Catalyzed Intramolecular Fluorocarbamoylation of Alkynes via Halide Recycling","abstract":"A BF 3 -catalyzed atom-economical fluorocarbamoylation reaction of alkyne-tethered carbamoyl fluorides is reported. The catalyst acts as both a fluoride source and Lewis acid activator, thereby enabling the formal insertion of alkynes into strong C–F bonds through a halide recycling mechanism. The developed method provides access to 3-(fluoromethylene) oxindoles and γ-lactams with excellent stereoselectivity, including fluorinated derivatives of known protein kinase inhibitors. Experimental and computational studies support a stepwise mechanism for the fluorocarbamoylation reaction involving a turnover-limiting cyclization step, followed by internal fluoride transfer from a BF 3 -coordinated carbamoyl adduct. For methylene oxindoles, a thermodynamically driven Z–E isomerization is facilitated by a transition state with aromatic character. In contrast, this aromatic stabilization is not relevant for γ-lactams, which results in a higher barrier for isomerization and the exclusive formation of the Z -isomer.","journal":"Journal of the American Chemical Society","year":2023,"id":330737,"datarank":0.5570358100056463,"base_score":3.713572066704308,"endowment":3.713572066704308,"self_citation_contribution":0.5570358100056463,"citation_network_contribution":0.0,"self_endowment_contribution":0.5570358100056463,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":40,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9454,"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":1055002,"name":"Ramon Arora","orcid":"0000-0003-4585-4328","position":1,"is_corresponding":false},{"id":1055003,"name":"Ekadashi Pradhan","orcid":"0000-0002-5087-3761","position":2,"is_corresponding":false},{"id":1055604,"name":"Yuriko H. Fujisato","orcid":null,"position":3,"is_corresponding":false},{"id":1055004,"name":"Ayonitemi J. Ajayi","orcid":"0000-0002-0731-0461","position":4,"is_corresponding":false},{"id":1055005,"name":"Mark Lautens","orcid":"0000-0002-0179-2914","position":5,"is_corresponding":false},{"id":478756,"name":"Tao Zeng","orcid":"0000-0002-1553-7850","position":6,"is_corresponding":false},{"id":864544,"name":"Christine M. Le","orcid":"0000-0003-2543-4414","position":7,"is_corresponding":false},{"id":1055001,"name":"E. Ali McKnight","orcid":"0000-0003-4289-4893","position":0,"is_corresponding":true}],"reference_count":72,"raw_metadata":{"citation_network_status":"fetched"},"created_at":"2026-07-19T01:09:14.691473Z","pmid":"37172320","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":[]}