{"doi":"10.1021/jacs.5c05409","title":"Total Synthesis of (−)-Illisimonin A Enabled by Pattern Recognition and Olefin Transposition","abstract":"High Resolution Image Download MS PowerPoint Slide We report an asymmetric total synthesis of (−)-illisimonin A, a sesquiterpene natural product with neurotrophic activity. Illisimonin A possesses a unique cage-like 5/5/5/5/5 pentacyclic scaffold containing a trans -pentalene and a norbornane, two highly strained and challenging structural motifs. It also contains seven contiguous fully substituted stereocenters, including three all-carbon quaternary centers, two of which are adjacent. Our synthesis exploits a pattern recognition strategy to identify a 5,6-fused bicyclic intermediate derived from ( S )-carvone in two steps as the starting point and leverages five sequential olefin transposition reactions to decorate the bicyclic carbocycle. Other key steps include a tandem Mukaiyama hydration-translactonization to form the γ-butyrolactone and an intramolecular aldol cyclization to close the cage and finally deliver (−)-illisimonin A in 16 steps.","journal":"Journal of the American Chemical Society","year":2025,"id":515499,"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":15,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9525,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2025-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1234131,"name":"Ziyao Zhang","orcid":"0009-0009-8377-6173","position":1,"is_corresponding":false},{"id":411172,"name":"Mingji Dai","orcid":"0000-0001-7956-6426","position":2,"is_corresponding":false},{"id":1234130,"name":"Bo Xu","orcid":"0000-0002-8872-3769","position":0,"is_corresponding":true}],"reference_count":51,"raw_metadata":null,"created_at":"2026-07-19T02:48:39.436300Z","pmid":"40358547","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":[]}