{"doi":"10.1021/jo048314i","title":"A Study of Vinyl Radical Cyclization Using <i>N</i>-Alkenyl-7-bromo-Substituted Hexahydroindolinones","abstract":null,"journal":"The Journal of Organic Chemistry","year":2005,"id":627748,"datarank":0.5333022092234121,"base_score":3.5553480614894135,"endowment":3.5553480614894135,"self_citation_contribution":0.5333022092234121,"citation_network_contribution":0.0,"self_endowment_contribution":0.5333022092234121,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":34,"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":1624942,"name":"Paitoon Rashatasakhon","orcid":null,"position":1,"is_corresponding":false},{"id":1624943,"name":"Ayse Daut Ozdemir","orcid":null,"position":2,"is_corresponding":false},{"id":1624944,"name":"Jerremey Willis","orcid":null,"position":3,"is_corresponding":false},{"id":1624940,"name":"Albert Padwa","orcid":null,"position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"A Study of Vinyl Radical Cyclization Using <i>N</i>-Alkenyl-7-bromo-Substituted Hexahydroindolinones","abstract":"A new method for the synthesis of the octahydropyrrolo[3,2,1-ij]quinoline ring system that possesses the characteristic skeleton of the aspidosperma family of alkaloids has been developed. The method utilizes an intramolecular Diels-Alder reaction of an amido-substituted furan across a tethered indole pi-bond. To apply this strategy to the synthesis of the indole alkaloid spegazzinidine, it was necessary to address the problem of assembling the final D-ring of the pentacyclic skeleton. Radical cyclization of a model N-allyl-7-bromo-3a-methylhexahydroindolinone system was found to preferentially lead to the 6-endo-trig cyclization product, with the best yield being obtained under high dilution conditions. The six-membered cyclized product is generated through two reaction pathways: (a) 6-endo-trig ring closure and (b) rearrangement of an intermediate methylene-cyclopentyl radical obtained by 5-exo-trig cyclization. A number of related 7-bromo-substituted hexahydroindolinones containing tethered olefinic groups were prepared and found to undergo efficient cyclization under both radical and palladium-mediated reaction conditions. Vinyl radical cyclization with several N-butenyl-substituted systems afforded a mixture of 6-exo and 7-endo cyclization products. A protocol to introduce an ethyl substituent into the C20-position of the aspidospermidine skeleton was also developed.","is_dataset_classified":null,"base_score":3.5553480614894135,"endowment":3.5553480614894135,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"15651796","pmcid":null,"openalex_id":"https://openalex.org/W2089780700","authors":[],"funders":[{"funder_name":"NCRR NIH HHS","grant_id":"S10-RR13673","title":null}],"total_grants":1,"fwci":1.5369,"citation_percentile":0.80207053,"influential_citations":0,"citation_trend":[{"year":2012,"count":1},{"year":2013,"count":1},{"year":2014,"count":2},{"year":2015,"count":1},{"year":2016,"count":2},{"year":2017,"count":2},{"year":2019,"count":4},{"year":2020,"count":3},{"year":2021,"count":3},{"year":2024,"count":1},{"year":2026,"count":1}],"oa_status":"closed","license":null,"oa_locations":[{"url":"https://pubs.acs.org/doi/pdf/10.1021/jo048314i","host_type":"publisher"},{"url":"https://doi.org/10.1021/jo048314i","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/15651796","host_type":"repository"}],"fields_of_study":["Advanced Synthetic Organic Chemistry","Chemical synthesis and alkaloids","Synthesis and Reactivity of Heterocycles","Alkaloids","Cyclization","Free Radicals","Indoles","Molecular Structure","Palladium"],"mesh_terms":["Alkaloids","Cyclization","Free Radicals","Indoles","Palladium","Molecular Structure"],"keywords":["Chemistry","Radical cyclization","Indole test","Ring (chemistry)","Furan","Substituent","Intramolecular force","Intramolecular reaction","Free-radical reaction","Total synthesis","Yield (engineering)","Medicinal chemistry","Stereochemistry","Radical","Organic chemistry"],"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":"2026-08-04T18:44:55.199706Z","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":[]}