biostudies-literatureJiang LMarie Skłodowska-Curie ActionsEuropean Research CouncilAgencia Estatal de Investigacion4327-4333https://www.ebi.ac.uk/biostudies/studies/S-EPMC9006967biostudies-literatureUnknown13(15)Herein we describe the first construction of fluorinated tertiary stereocenters based on an alkene C(sp²)-C(sp²) bond cleavage. The new process, that takes advantage of a Rh-catalyzed carbyne transfer, relies on a branched-selective fluorination of tertiary allyl cations and is distinguished by a wide scope including natural products and drug molecule derivatives as well as adaptability to radiofluorination.Chemical scienceCatalytic alkene skeletal modification for the construction of fluorinated tertiary stereocenters.PMC9006967101028657EUR2019-103814PID2020-117656RB-100Maria de Maeztu Excellence Accreditation MDM-2017-0720BES-2017-080163ERC-CoG 2019, 865554PID2019-104101GB-I00Severo Ochoa Excellence Accreditation 2020–2023 -CEX2019- 000925-S865554794815Jiang LSarro PSuero MGTeo WJLlop JfalseCatalytic alkene skeletal modification for the construction of fluorinated tertiary stereocenters.Herein we describe the first construction of fluorinated tertiary stereocenters based on an alkene C(sp²)-C(sp²) bond cleavage. The new process, that takes advantage of a Rh-catalyzed carbyne transfer, relies on a branched-selective fluorination of tertiary allyl cations and is distinguished by a wide scope including natural products and drug molecule derivatives as well as adaptability to radiofluorination.2022-01-01T00:00:00Z2022 Apr2024-12-04T09:13:43.308Z2024-12-04T09:13:43.308ZS-EPMC90069673550947210.1039/d2sc00968d