{"doi":"10.1021/ja903277d","title":"Revealing a Second Transmetalation Step in the Negishi Coupling and Its Competition with Reductive Elimination: Improvement in the Interpretation of the Mechanism of Biaryl Syntheses","abstract":null,"journal":"Journal of the American Chemical Society","year":2009,"id":607045,"datarank":0.7846662925281881,"base_score":5.231108616854587,"endowment":5.231108616854587,"self_citation_contribution":0.7846662925281881,"citation_network_contribution":0.0,"self_endowment_contribution":0.7846662925281881,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":186,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":null,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":null,"fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":956914,"name":"Yu Lan","orcid":"0000-0003-0373-1944","position":1,"is_corresponding":false},{"id":610107,"name":"Jing Liu","orcid":"0000-0002-6805-8503","position":2,"is_corresponding":false},{"id":597457,"name":"Gang Li","orcid":"0000-0001-8796-7510","position":3,"is_corresponding":false},{"id":1558593,"name":"Yun-Dong Wu","orcid":null,"position":4,"is_corresponding":false},{"id":1558594,"name":"Aiwen Lei","orcid":null,"position":5,"is_corresponding":false},{"id":539298,"name":"Qiang Liu","orcid":"0000-0002-7668-6868","position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"Revealing a Second Transmetalation Step in the Negishi Coupling and Its Competition with Reductive Elimination: Improvement in the Interpretation of the Mechanism of Biaryl Syntheses","abstract":"This paper presents an experimental and theoretical investigation of the Pd-catalyzed Negishi coupling reaction and reveals a novel second transmetalation reaction between an Ar(1)-Pd-Ar(2) species and the organozinc reagent Ar(2)-ZnX. Understanding of this second step reveals how homocoupling and dehalogenation products are formed. Thus, the second transmetalation generates Ar(2)PdAr(2) and Ar(1)ZnCl, which upon reductive elimination and hydrolysis, respectively, give the homocoupling product Ar(2)-Ar(2) and the dehalogenation product Ar(1)H. The ratio of the cross-coupling product Ar(1)-Ar(2) and the homocoupling product Ar(2)-Ar(2) is determined by competition between the second transmetalation and reductive elimination steps. This mechanism is further supported by density functional theoretical calculations. Calculations on a series of reactions suggest a strategy in controlling the selectivity of cross-coupling and homocoupling pathways, which we have experimentally verified.","is_dataset_classified":null,"base_score":5.231108616854587,"endowment":5.231108616854587,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"19572717","pmcid":null,"openalex_id":"https://openalex.org/W2160923546","authors":[],"funders":[],"total_grants":0,"fwci":8.3329,"citation_percentile":0.98445867,"influential_citations":0,"citation_trend":[{"year":2012,"count":21},{"year":2013,"count":17},{"year":2014,"count":15},{"year":2015,"count":16},{"year":2016,"count":11},{"year":2017,"count":16},{"year":2018,"count":11},{"year":2019,"count":11},{"year":2020,"count":6},{"year":2021,"count":8},{"year":2022,"count":6},{"year":2023,"count":3},{"year":2024,"count":2},{"year":2025,"count":6},{"year":2026,"count":5}],"oa_status":"closed","license":null,"oa_locations":[{"url":"https://pubs.acs.org/doi/pdf/10.1021/ja903277d","host_type":"publisher"},{"url":"https://doi.org/10.1021/ja903277d","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/19572717","host_type":"repository"},{"url":"http://repository.hkust.edu.hk/ir/Record/1783.1-18041","host_type":"repository"}],"fields_of_study":["Catalytic Cross-Coupling Reactions","Catalytic C–H Functionalization Methods","Asymmetric Hydrogenation and Catalysis","Benzene Derivatives","Models, Molecular","Molecular Structure","Organometallic Compounds","Palladium","Time Factors"],"mesh_terms":["Benzene Derivatives","Models, Molecular","Organometallic Compounds","Palladium","Time Factors","Molecular Structure"],"keywords":["Transmetalation","Chemistry","Negishi coupling","Reductive elimination","Halogenation","Reagent","Reaction mechanism","Computational chemistry","Metalation","Combinatorial chemistry","Organic chemistry","Catalysis"],"sdg_mappings":[],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-07-30T05:39:13.005112Z","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":[]}