{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Lin LQH"],"funding":["Ministry of Education - Singapore","Welch Foundation","National Institutes of Health","NIH HHS","NIGMS NIH HHS"],"pagination":["e202317935"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC11076007"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["63(7)"],"pubmed_abstract":["An emerging class of C-C coupling transformations that furnish drug-like building blocks involves catalytic hydrocarbonation of alkenes. However, despite notable advances in the field, hydrocarbon addition to gem-difluoroalkenes without additional electronic activation remains largely unsuccessful. This owes partly to poor reactivity and the propensity of difluoroalkenes to undergo defluorinative side reactions. Here, we report a nickel catalytic system that promotes efficient 1,2-selective hydroarylation and hydroalkenylation, suppressing defluorination and providing straightforward access to a diverse assortment of prized organofluorides bearing difluoromethyl-substituted carbon centers. In contrast to radical-based pathways and reactions triggered by hydrometallation via a nickel-hydride complex, our experimental and computational studies support a mechanism in which a catalytically active nickel-bromide species promotes selective carbonickelation with difluoroalkenes followed by alkoxide exchange and hydride transfer, effectively overcoming the difluoroalkene's intrinsic electronic bias."],"journal":["Angewandte Chemie (International ed. in English)"],"pubmed_title":["Selective 1,2-Hydroarylation(Alkenylation) of gem-Difluoroalkenes to Access (-CF<sub>2</sub> H) Motifs."],"pmcid":["PMC11076007"],"funding_grant_id":["R35 GM137797","A-2102-20220331","A-8000034-00-00","R35GM137797"],"pubmed_authors":["Lin LQH","Renteria-Gomez A","Gutierrez O","Zhang YQ","Parris AB","Ong KZW","Martin RT","Koh MJ"],"additional_accession":[]},"is_claimable":false,"name":"Selective 1,2-Hydroarylation(Alkenylation) of gem-Difluoroalkenes to Access (-CF<sub>2</sub> H) Motifs.","description":"An emerging class of C-C coupling transformations that furnish drug-like building blocks involves catalytic hydrocarbonation of alkenes. However, despite notable advances in the field, hydrocarbon addition to gem-difluoroalkenes without additional electronic activation remains largely unsuccessful. This owes partly to poor reactivity and the propensity of difluoroalkenes to undergo defluorinative side reactions. Here, we report a nickel catalytic system that promotes efficient 1,2-selective hydroarylation and hydroalkenylation, suppressing defluorination and providing straightforward access to a diverse assortment of prized organofluorides bearing difluoromethyl-substituted carbon centers. In contrast to radical-based pathways and reactions triggered by hydrometallation via a nickel-hydride complex, our experimental and computational studies support a mechanism in which a catalytically active nickel-bromide species promotes selective carbonickelation with difluoroalkenes followed by alkoxide exchange and hydride transfer, effectively overcoming the difluoroalkene's intrinsic electronic bias.","dates":{"release":"2024-01-01T00:00:00Z","publication":"2024 Feb","modification":"2025-04-18T13:01:21.83Z","creation":"2025-04-06T22:29:38.035Z"},"accession":"S-EPMC11076007","cross_references":{"pubmed":["38117662"],"doi":["10.1002/anie.202317935"]}}