{"doi":"10.1021/acsomega.4c00909","title":"A Comparative Study of Cationic Copper(I) Reagents Supported by Bipodal Tetramethylguanidinyl-Containing Ligands as Nitrene-Transfer Catalysts","abstract":"High Resolution Image Download MS PowerPoint Slide The bipodal compounds [(TMG 2 biphen N-R )Cu I –NCMe](PF 6 ) (R = Me, Ar (4-CF 3 Ph-)) and [(TMG 2 biphen N-Me )Cu I –I] have been synthesized with ligands that feature a diarylmethyl- and triaryl-amine framework and superbasic tetramethylguanidinyl residues (TMG). The cationic Cu(I) sites mediate catalytic nitrene-transfer reactions between the imidoiodinane PhI = NTs (Ts = tosyl) and a panel of styrenes in MeCN, to afford aziridines, demonstrating comparable reactivity profiles. The copper reagents have been further explored to execute C–H amination reactions with a variety of aliphatic and aromatic hydrocarbons and two distinct nitrene sources PhI = NTs and PhI = NTces (Tces = 2,2,2-trichloroethylsulfamate) in benzene/HFIP (10:2 v/v). Good yields have been obtained for sec-benzylic and tert-C–H bonds of various substrates, especially with the more electron-deficient catalyst [(TMG 2 biphen N–Ar )Cu I –NCMe](PF 6 ). In conjunction with earlier studies, the order of reactivity of these bipodal cationic reagents as a function of the metal employed is established as Cu > Fe > Co ≥ Mn. However, as opposed to the base-metal analogues, the bipodal Cu reagents are less reactive than a similar tripodal Cu catalyst. The observed fluorophilicity of the bipodal Cu compounds may provide a deactivation pathway.","journal":"ACS Omega","year":2024,"id":467593,"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":3,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9399,"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":1110132,"name":"Brent Harfmann","orcid":"0009-0009-7865-8930","position":1,"is_corresponding":false},{"id":1300253,"name":"Himanshu Bhatia","orcid":"0009-0004-4211-2104","position":2,"is_corresponding":false},{"id":1300254,"name":"Harish Singh","orcid":"0000-0003-4870-1159","position":3,"is_corresponding":false},{"id":1300255,"name":"Srikanth Balijapelly","orcid":"0000-0003-2720-8568","position":4,"is_corresponding":false},{"id":1110134,"name":"Amitava Choudhury","orcid":"0000-0001-5496-7346","position":5,"is_corresponding":false},{"id":768225,"name":"Pericles Stavropoulos","orcid":"0000-0003-0985-6203","position":6,"is_corresponding":false},{"id":1110131,"name":"Suraj Kumar Sahoo","orcid":"0000-0003-3835-1706","position":0,"is_corresponding":true}],"reference_count":116,"raw_metadata":null,"created_at":"2026-07-19T02:05:15.025255Z","pmid":"38585072","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":[]}