{"doi":"10.1021/jacs.4c01857","title":"Leveraging the Stereochemical Complexity of Octahedral Diastereomeric-at-Metal Catalysts to Unlock Regio-, Diastereo-, and Enantioselectivity in Alcohol-Mediated C–C Couplings via Hydrogen Transfer","abstract":"Experimental and computational studies illuminating the factors that guide metal-centered stereogenicity and, therefrom, selectivity in transfer hydrogenative carbonyl additions of alcohol proelectrophiles catalyzed by chiral-at-metal-and-ligand octahedral d 6 metal ions, iridium(III) and ruthenium(II), are described. To augment or invert regio-, diastereo-, and enantioselectivity, predominantly one from among as many as 15 diastereomeric-at-metal complexes is required. For iridium(III) catalysts, cyclometalation assists in defining the metal stereocenter, and for ruthenium(II) catalysts, iodide counterions play a key role. Whereas classical strategies to promote selectivity in metal catalysis aim for high-symmetry transition states, well-defined low-symmetry transition states can unlock selectivities that are otherwise difficult to achieve or inaccessible.","journal":"Journal of the American Chemical Society","year":2024,"id":424957,"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":20,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.949,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2024-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1060298,"name":"Catherine G. Santana","orcid":"0000-0001-8135-0149","position":1,"is_corresponding":false},{"id":677869,"name":"Eliezer Ortiz","orcid":"0000-0002-7349-6081","position":2,"is_corresponding":false},{"id":886246,"name":"Cole C. Meyer","orcid":"0000-0002-4319-7806","position":3,"is_corresponding":false},{"id":285942,"name":"Peng Liu","orcid":"0000-0002-8188-632X","position":4,"is_corresponding":false},{"id":1083694,"name":"Ken Sakata","orcid":"0000-0002-6920-0735","position":5,"is_corresponding":false},{"id":233308,"name":"Kuo‐Wei Huang","orcid":"0000-0003-1900-2658","position":6,"is_corresponding":false},{"id":596116,"name":"Michael J. Krische","orcid":"0000-0001-8418-9709","position":7,"is_corresponding":false},{"id":854337,"name":"Jonathan Z. Shezaf","orcid":"0000-0003-4865-5973","position":0,"is_corresponding":true}],"reference_count":129,"raw_metadata":null,"created_at":"2026-07-19T01:58:21.523756Z","pmid":"38478891","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":[]}