{"doi":"10.1021/jacs.3c06734","title":"Chiral-at-Ruthenium-SEGPHOS Catalysts Display Diastereomer-Dependent Regioselectivity: Enantioselective Isoprene-Mediated Carbonyl <i>tert</i>-Prenylation via Halide Counterion Effects","abstract":"The first correlation between metal-centered stereogenicity and regioselectivity in a catalytic process is described. Alternate pseudo -diastereomeric chiral-at-ruthenium complexes of the type RuX(CO)[η 3 -prenyl][( S )-SEGPHOS] form in a halide-dependent manner and display divergent regioselectivity in catalytic C–C couplings of isoprene to alcohol proelectrophiles via hydrogen autotransfer. Whereas the chloride-bound ruthenium-SEGPHOS complex prefers a trans -relationship between the halide and carbonyl ligands and delivers products of carbonyl sec -prenylation, the iodide-bound ruthenium-SEGPHOS complex prefers a cis -relationship between the halide and carbonyl ligands and delivers products of carbonyl tert -prenylation. The chloride- and iodide-bound ruthenium-SEGPHOS complexes were characterized in solution and solid phase by 31 P NMR and X-ray diffraction. Density functional theory calculations of the iodide-bound catalyst implicate a Curtin–Hammett-type scenario in which the transition states for aldehyde coordination from an equilibrating mixture of sec - and tert -prenylruthenium complexes are rate- and product-determining. Thus, control of metal-centered diastereoselectivity has unlocked the first catalytically enantioselective isoprene-mediated carbonyl tert -prenylations.","journal":"Journal of the American Chemical Society","year":2023,"id":344802,"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":13,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9496,"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":1060298,"name":"Catherine G. Santana","orcid":"0000-0001-8135-0149","position":1,"is_corresponding":false},{"id":1060958,"name":"Connor Saludares","orcid":null,"position":2,"is_corresponding":false},{"id":1084176,"name":"Edward S. Briceno","orcid":null,"position":3,"is_corresponding":false},{"id":1083694,"name":"Ken Sakata","orcid":"0000-0002-6920-0735","position":4,"is_corresponding":false},{"id":596116,"name":"Michael J. Krische","orcid":"0000-0001-8418-9709","position":5,"is_corresponding":false},{"id":854337,"name":"Jonathan Z. Shezaf","orcid":"0000-0003-4865-5973","position":0,"is_corresponding":true}],"reference_count":49,"raw_metadata":null,"created_at":"2026-07-19T01:11:35.133818Z","pmid":"37555765","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":[]}