{"doi":"10.1021/jacs.3c00934","title":"Dual Ruthenium-Catalyzed Alkene Isomerization–Hydrogen Auto-Transfer Unlocks Skipped Dienes as Pronucleophiles for Enantioselective Alcohol C–H Allylation","abstract":"The first use of 1,4-pentadiene and 1,5-hexadiene as allylmetal pronucleophiles in regio-, anti -diastereo-, and enantioselective carbonyl addition from alcohol proelectrophiles is described. As corroborated by deuterium labeling experiments, primary alcohol dehydrogenation delivers a ruthenium hydride that affects alkene isomerization to furnish a conjugated diene, followed by transfer hydrogenative carbonyl addition. Hydrometalation appears to be assisted by the formation of a fluxional olefin-chelated homoallylic alkylruthenium complex II, which exists in equilibrium with its pentacoordinate η 1 form to enable β-hydride elimination. This effect confers remarkable chemoselectivity: while 1,4-pentadiene and 1,5-hexadiene are competent pronucleophiles, higher 1, n -dienes are not, and the olefinic functional groups of the products remain intact under conditions in which the 1,4- and 1,5-dienes isomerize. A survey of halide counterions reveals iodide-bound ruthenium-JOSIPHOS catalysts are uniquely effective in these processes. This method was used to prepare a previously reported C1–C7 substructure of (−)-pironetin in 4 vs 12 steps.","journal":"Journal of the American Chemical Society","year":2023,"id":369308,"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":9,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9491,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2023-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":870315,"name":"Weijia Shen","orcid":"0000-0001-6345-3371","position":1,"is_corresponding":false},{"id":1127991,"name":"John A. Little","orcid":"0000-0001-5896-138X","position":2,"is_corresponding":false},{"id":596116,"name":"Michael J. Krische","orcid":"0000-0001-8418-9709","position":3,"is_corresponding":false},{"id":714062,"name":"Zachary J. Dubey","orcid":"0000-0003-3009-5947","position":0,"is_corresponding":true}],"reference_count":89,"raw_metadata":null,"created_at":"2026-07-19T01:15:28.704894Z","pmid":"37018070","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":[]}