{"doi":"10.1021/jacs.4c06071","title":"Synthesis of <i>Z</i>-<i>gem</i>-Cl,CF<sub>3</sub>-Substituted Alkenes by Stereoselective Cross-Metathesis and the Role of Disubstituted Mo Alkylidenes","abstract":"Stereochemically defined organofluorine compounds are central to drug discovery and development. Here, we present a catalytic cross-metathesis method for the synthesis of Z -trisubstituted olefins that contain a Cl- and a CF 3 -bound carbon terminus. Notably, the process is stereo selective, which is in contrast to the existing stereoretentive strategies that also involve a trisubstituted olefin as starting material. Reactions are catalyzed by a Mo monoaryloxide pyrrolide alkylidene, involve a trisubstituted alkene and gem -Cl,CF 3 -substituted alkene, and are fully Z -selective. Catalytic cross-coupling can be used to convert the C–Cl bond of the trisubstituted olefin to C–B, C–D, and different C–C bonds. We elucidate the role of Cl,CF 3 -disubstituted Mo alkylidenes. Experimental and computational (DFT) data show that in some instances a disubstituted alkylidene is formed and then transformed to a more active complex. In other cases, the Cl,CF 3 -disubstituted alkylidene is a direct participant in a catalytic cycle. The studies described shed new light on the chemistry of high oxidation-state disubstituted alkylidenes–scarcely investigated entities likely to be pivotal to approaches for stereocontrolled synthesis of tetrasubstituted alkenes through olefin metathesis.","journal":"Journal of the American Chemical Society","year":2024,"id":453784,"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":8,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9493,"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":1032149,"name":"Can Qin","orcid":"0000-0002-1565-1442","position":1,"is_corresponding":false},{"id":1276646,"name":"Jing Wan","orcid":"0000-0002-3793-868X","position":2,"is_corresponding":false},{"id":492205,"name":"Binh Khanh","orcid":"0000-0001-8487-1417","position":3,"is_corresponding":false},{"id":1032150,"name":"Xin Zhi Sui","orcid":"0000-0001-7435-2381","position":4,"is_corresponding":false},{"id":1277073,"name":"Haruki Kobayashi","orcid":null,"position":5,"is_corresponding":false},{"id":1277074,"name":"Hossein Zahedian","orcid":null,"position":6,"is_corresponding":false},{"id":285942,"name":"Peng Liu","orcid":"0000-0002-8188-632X","position":7,"is_corresponding":false},{"id":308976,"name":"Amir H. Hoveyda","orcid":"0000-0002-1470-6456","position":8,"is_corresponding":false},{"id":869840,"name":"Qinghe Liu","orcid":"0000-0003-3125-7135","position":0,"is_corresponding":true}],"reference_count":66,"raw_metadata":null,"created_at":"2026-07-19T02:03:03.428151Z","pmid":"39078367","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":[]}