{"doi":"10.1021/jacs.2c07489","title":"Copper Hydride-Catalyzed Enantioselective Olefin Hydromethylation","abstract":null,"journal":"Journal of the American Chemical Society","year":2022,"id":659456,"datarank":0.5955437870328184,"base_score":3.970291913552122,"endowment":3.970291913552122,"self_citation_contribution":0.5955437870328184,"citation_network_contribution":0.0,"self_endowment_contribution":0.5955437870328184,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":52,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":null,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":null,"fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1005063,"name":"Kwangmin Shin","orcid":"0000-0002-1708-2351","position":1,"is_corresponding":false},{"id":492205,"name":"Binh Khanh","orcid":"0000-0001-8487-1417","position":2,"is_corresponding":false},{"id":285942,"name":"Peng Liu","orcid":"0000-0002-8188-632X","position":3,"is_corresponding":false},{"id":285943,"name":"Stephen L. Buchwald","orcid":"0000-0003-3875-4775","position":4,"is_corresponding":false},{"id":400389,"name":"Yuyang Dong","orcid":"0000-0002-4533-4798","position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"Copper Hydride-Catalyzed Enantioselective Olefin Hydromethylation.","abstract":"The enantioselective installation of a methyl group onto a small molecule can result in the significant modification of its biological properties. While hydroalkylation of olefins represents an attractive approach to introduce alkyl substituents, asymmetric hydromethylation protocols are often hampered by the incompatibility of highly reactive methylating reagents and a lack of general applicability. Herein, we report an asymmetric olefin hydromethylation protocol enabled by CuH catalysis. This approach leverages methyl tosylate as a methyl source compatible with the reducing base-containing reaction environment, while a catalytic amount of iodide ion transforms the methyl tosylate <i>in situ</i> into the active reactant, methyl iodide, to promote the hydromethylation. This method tolerates a wide range of functional groups, heterocycles, and pharmaceutically relevant frameworks. Density functional theory studies suggest that after the stereoselective hydrocupration, the methylation step is stereoretentive, taking place through an S<sub>N</sub>2-type oxidative addition mechanism with methyl iodide followed by a reductive elimination.","is_dataset_classified":null,"base_score":0.0,"endowment":0.0,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"36044255","pmcid":"PMC9994624","openalex_id":null,"authors":[],"funders":[{"funder_name":"NIGMS NIH HHS","grant_id":"R35 GM122483","title":null},{"funder_name":"NIGMS NIH HHS","grant_id":"R01 GM058160","title":null},{"funder_name":"National Institute of General Medical Sciences","grant_id":"GM058160-17S1","title":null},{"funder_name":"NIGMS NIH HHS","grant_id":"R35 GM128779","title":null},{"funder_name":"National Institute of General Medical Sciences","grant_id":"R35-GM122483","title":null},{"funder_name":"Division of Advanced Cyberinfrastructure","grant_id":"ACI-1548562","title":null},{"funder_name":"National Institutes of Health","grant_id":"5R35GM128779-07","title":"Computational Models for Reactivity and Selectivity in Catalytic Olefin Functionalization"},{"funder_name":"National Institutes of Health","grant_id":"3R35GM122483-08S1","title":"Administrative Supplement for Equipment"}],"total_grants":8,"fwci":null,"citation_percentile":null,"influential_citations":0,"citation_trend":[],"oa_status":"green","license":"CC BY NC ND","oa_locations":[{"url":"https://www.ncbi.nlm.nih.gov/pmc/articles/9994624","host_type":"repository"},{"url":"https://doi.org/10.26434/chemrxiv-2022-s3n7v","host_type":""},{"url":"https://doi.org/10.1021/jacs.2c07489","host_type":""},{"url":"https://pubmed.ncbi.nlm.nih.gov/36044255","host_type":""}],"fields_of_study":["01 natural sciences","0104 chemical sciences"],"mesh_terms":["Copper","Alkenes","Benzenesulfonates","Hydrocarbons, Iodinated","Catalysis","Stereoisomerism"],"keywords":["Benzenesulfonates","Stereoisomerism","Alkenes","Hydrocarbons, Iodinated","Catalysis","Copper"],"sdg_mappings":[],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-08-12T06:57:32.563201Z","pmid":null,"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":[]}