Markovnikov hydroamination of terminal alkenes via phosphine redox catalysis

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Article Published: 23 February 2026 Nature (2026)Cite this article We are providing an unedited version of this manuscript to give early access to its findings. Before final publication, the manuscript will undergo further editing. Please note there may be errors present which affect the content, and all legal disclaimers apply. AbstractMain-group catalysts that mimic transition metal reactivity can expand substrate tolerance and enable transformations not currently possible with metal catalysis1. The discovery that PIII and PV phosphorus intermediates can undergo transition metal-like two-electron chemistry raises the question whether radical PIV intermediates can mimic other elementary steps in organometallic chemistry2,3. Here we describe a phosphine-photoredox catalyst system that promotes intermolecular Markovnikov hydroamination of unactivated terminal alkenes with numerous classes of N–H azoles, a reaction that is not possible with late transition metal catalysis. Experimental and computational mechanistic studies support a new elementary step for main group catalysis wherein a phosphine radical cation activates the alkene to nucleophilic amination by the azole, a step otherwise associated with transition metals. Given the broad value of nucleophilic alkene functionalization in transition metal catalysis, this PIV mechanism could offer new opportunities for main group element catalysis and chemical synthesis. This is a preview of subscription content, access via your institution Access options Access Nature and 54 other Nature Portfolio journals Get Nature+, our best-value online-access subscription $32.99 / 30 days cancel any time Subscribe to this journal Receive 51 print issues and online access $199.00 per year only $3.90 per issue Rent or buy this article Prices vary by article type from$1.95 to$39.95 Prices may be subject to local taxes which are calculated during checkout Additional access options: Log in Learn about institutional subscriptions Read our FAQs Contact customer support Author informationAuthors and AffiliationsDepartment of Chemistry & Biochemistry, University of California, Los Angeles, California, USAFlora Fan, Alexander J. Maertens & Abigail G. DoyleDepartment of Chemistry, Princeton University, Princeton, New Jersey, USAKassandra F. SedilloAuthorsFlora FanKassandra F. SedilloAlexander J. MaertensAbigail G. DoyleCorresponding authorCorrespondence to Abigail G. Doyle.Supplementary informationSupplementary InformationSupplementary Information, containing the following sections:1. General Information; 2. Control Experiments and Reaction Optimization; 3. Functional Group Robustness Screen; 4. General Procedure B and Characterization; 5. Other Procedures and Characterization; 6. X-ray Crystal Structure; 7. Evaluation of Byproducts; 8. Synthesis of Alkenes; 9. Mechanistic Investigations; 10. DFT Studies; 11. References; 12. NMR Characterization.Peer Review FileAbout this articleCite this articleFan, F., Sedillo, K.F., Maertens, A.J. et al. Markovnikov hydroamination of terminal alkenes via phosphine redox catalysis. Nature (2026). https://doi.org/10.1038/s41586-026-10263-7Download citationReceived: 25 August 2025Accepted: 11 February 2026Published: 23 February 2026DOI: https://doi.org/10.1038/s41586-026-10263-7