{"doi":"10.1021/jo049542f","title":"Competing Pathways in the [2 + 2] Cycloadditions of Cyclopentyne and Benzyne. A DFT and ab Initio Study","abstract":null,"journal":"The Journal of Organic Chemistry","year":2004,"id":677162,"datarank":0.47670807455219194,"base_score":3.1780538303479458,"endowment":3.1780538303479458,"self_citation_contribution":0.47670807455219194,"citation_network_contribution":0.0,"self_endowment_contribution":0.47670807455219194,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":23,"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":1769310,"name":"Armagan Kinal","orcid":null,"position":1,"is_corresponding":false},{"id":1769307,"name":"Ilker Ozkan","orcid":null,"position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"Competing Pathways in the [2 + 2] Cycloadditions of Cyclopentyne and Benzyne. A DFT and ab Initio Study","abstract":"The [2 + 2] cycloadditions of cyclopentyne and benzyne to ethylene are explored at the B3LYP and CASSCF levels, supplemented by CCSD(T) and CAS-MP2 calculations at the stationary points. The biradical path in the benzyne system is computed to be about 4.1 kcal/mol lower than the concerted path, consistent with the experimentally observed loss of original stereochemistry in this cycloaddition. However, computations fail to confirm the 99% stereoretention in the corresponding reaction of cyclopentyne. The concerted and biradical paths in the latter reaction are found to involve nearly isoenergetic barriers, thus predicting only about 75% stereoretention. More sophisticated theoretical methods seem to be needed to resolve the issue in the cyclopentyne system.","is_dataset_classified":null,"base_score":3.1780538303479458,"endowment":3.1780538303479458,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"15287786","pmcid":null,"openalex_id":"https://openalex.org/W1987582703","authors":[],"funders":[],"total_grants":0,"fwci":1.3999,"citation_percentile":0.79573688,"influential_citations":0,"citation_trend":[{"year":2014,"count":1},{"year":2015,"count":2},{"year":2018,"count":1},{"year":2021,"count":3},{"year":2022,"count":2},{"year":2023,"count":2}],"oa_status":"closed","license":null,"oa_locations":[{"url":"https://pubs.acs.org/doi/pdf/10.1021/jo049542f","host_type":"publisher"},{"url":"https://doi.org/10.1021/jo049542f","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/15287786","host_type":"repository"},{"url":"https://hdl.handle.net/11511/31181","host_type":"repository"}],"fields_of_study":["Advanced Chemical Physics Studies","Cyclization and Aryne Chemistry","Organic Chemistry Cycloaddition Reactions"],"mesh_terms":[],"keywords":["Aryne","Chemistry","Cycloaddition","Computational chemistry","Ab initio","Ethylene","Ab initio quantum chemistry methods","Path (computing)","Reaction mechanism","Medicinal chemistry","Molecule","Organic chemistry","Catalysis"],"sdg_mappings":[{"sdg_number":0,"sdg_label":"Clean water and sanitation"}],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-08-17T03:42:56.951873Z","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":[]}