{"doi":"10.1002/ange.202209099","title":"Regio‐ and Stereoselective 1,2‐Oxyhalogenation of Non‐Conjugated Alkynes via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes**","abstract":"Abstract A catalytic 1,2‐oxyhalogenation method that converts non‐conjugated internal alkynes into tetrasubstituted alkenes with high regio‐ and stereoselectivity is described. Mechanistically, the reaction involves a Pd II /Pd IV catalytic cycle that begins with a directed oxypalladation step. The origin of regioselectivity is the preference for formation of a six‐membered palladacycle intermediate, which is facilitated by an N,N‐bidentate 2‐(pyridin‐2‐yl)isopropyl (PIP) amide directing group. Selectivity for C(alkenyl)−X versus −N (X=halide) reductive elimination from the Pd IV center depends on the identity of the halide anion; bromide and iodide engage in C(alkenyl)−X formation, while intramolecular C(alkenyl)−N reductive elimination occurs with chloride to furnish a lactam product. DFT calculations shed light on the origins of this phenomenon.","journal":"Angewandte Chemie","year":2022,"id":280063,"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":1,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9442,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2022-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":954115,"name":"Juntao Sun","orcid":"0000-0001-8973-1376","position":1,"is_corresponding":false},{"id":588922,"name":"Tao Zhang","orcid":"0009-0009-8039-5738","position":2,"is_corresponding":false},{"id":954116,"name":"Yi Ding","orcid":"0000-0002-4125-3552","position":3,"is_corresponding":false},{"id":954117,"name":"Ye‐Qiang Han","orcid":"0000-0002-6377-7998","position":4,"is_corresponding":false},{"id":812714,"name":"Raúl Martín‐Montero","orcid":null,"position":5,"is_corresponding":false},{"id":954118,"name":"Yu Lan","orcid":"0000-0002-2328-0020","position":6,"is_corresponding":false},{"id":615851,"name":"Bing‐Feng Shi","orcid":"0000-0003-0375-955X","position":7,"is_corresponding":false},{"id":315493,"name":"Keary M. Engle","orcid":"0000-0003-2767-6556","position":8,"is_corresponding":false},{"id":578451,"name":"Mingyu Liu","orcid":"0000-0003-4649-7393","position":0,"is_corresponding":true}],"reference_count":76,"raw_metadata":null,"created_at":"2026-07-19T00:28:59.341002Z","pmid":null,"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":[]}