{"doi":"10.1021/jacs.3c04376","title":"Net-1,2-Hydrogen Atom Transfer of Amidyl Radicals: Toward the Synthesis of 1,2-Diamine Derivatives","abstract":"Hydrogen atom transfer (HAT) processes are among the most useful approaches for the selective construction of C(sp 3 )–C(sp 3 ) bonds. 1,5-HAT with heteroatom-centered radicals (O •, N • ) have been well established and are favored relative to other 1, n -HAT processes. In comparison, net 1,2-HAT processes have been observed infrequently. Herein, the first amidyl radicalls are reported that preferentially undergo a net 1,2-HAT over 1,5-HAT. Beginning with single electron transfer from 2-azaallyl anions to N -alkyl N -aryloxy amides, the latter generate amidyl radicals. The amidyl radical undergoes a net-1,2-HAT to generate a C-centered radical that participates in an intermolecular radical–radical coupling with the 2-azaallyl radical to generate 1,2-diamine derivatives. Mechanistic and EPR experiments point to radical intermediates. Density functional theory calculations provide support for a base-assisted, stepwise-1,2-HAT process. It is proposed that the generation of amidyl radicals under basic conditions can be greatly expanded to access α-amino C-centered radicals that will serve as valuable synthetic intermediates.","journal":"Journal of the American Chemical Society","year":2023,"id":318420,"datarank":0.6307038929086449,"base_score":4.204692619390966,"endowment":4.204692619390966,"self_citation_contribution":0.6307038929086449,"citation_network_contribution":0.0,"self_endowment_contribution":0.6307038929086449,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":66,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9458,"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":1025659,"name":"Dongxiang Liu","orcid":"0000-0002-7639-5497","position":1,"is_corresponding":false},{"id":752193,"name":"Madeline E. Rotella","orcid":"0000-0002-7973-2452","position":2,"is_corresponding":false},{"id":1025660,"name":"Guogang Deng","orcid":"0009-0005-6102-326X","position":3,"is_corresponding":false},{"id":1025661,"name":"Zhengfen Liu","orcid":"0000-0002-3038-6165","position":4,"is_corresponding":false},{"id":1025662,"name":"Wen Chen","orcid":"0000-0002-7782-3879","position":5,"is_corresponding":false},{"id":1025663,"name":"Hongbin Zhang","orcid":"0000-0002-2516-2634","position":6,"is_corresponding":false},{"id":325869,"name":"Marisa C. Kozlowski","orcid":"0000-0002-4225-7125","position":7,"is_corresponding":false},{"id":647810,"name":"Patrick J. Walsh","orcid":"0000-0001-8392-4150","position":8,"is_corresponding":false},{"id":1025664,"name":"Xiaodong Yang","orcid":"0000-0002-8466-5418","position":9,"is_corresponding":false},{"id":1025658,"name":"Yonggang Jiang","orcid":"0000-0003-4632-5575","position":0,"is_corresponding":true}],"reference_count":78,"raw_metadata":{"citation_network_status":"fetched"},"created_at":"2026-07-19T01:07:01.300821Z","pmid":"37441806","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":[]}