Alcohol group migration by proximity-enhanced H atom abstraction | Nature

Subjects Synthetic chemistry methodology Photocatalysis Abstract Subtle changes in molecular structure can lead to profound changes in molecular function. However, even minor structural refinements can require the complete re-synthesis of a target molecule, adding time and cost to molecular design campaigns 1 . Recently, editing methods have emerged targeting subtle molecular perturbations, including atomic substitution, stereocenter inversion and functional group repositioning 2 . These precision tools hold the potential to streamline the optimization of molecular function by fine-tuning molecular structure. Here we report an editing method that enables the migration of common alcohol functional groups to proximal sites with predictable stereo- and regiochemical outcomes. The reaction proceeds through a 1,2-acyloxy radical migration step under reversible H atom transfer catalysis conditions promoted by excited state decatungstate polyanion. Proximity effects arising from non-covalent interactions between substrate and reagent enable efficient radical formation at polarity-mismatched positions. Application of this tool at a late synthetic stage allows for the precise re-positioning of alcohol functional groups, while integration with common alcohol group installation methods provides new synthetic strategies to access challenging oxygenation patterns. Access through your institution Buy or subscribe This is a preview of subscription content, access via your institution Access options Access through your institution Access Nature and 54 other Nature Portfolio journals Get Nature+, our best-value online-access subscription $32.99 / 30 days cancel any time Learn more Subscribe to this journal Receive 51 print issues and online access $199.00 per year only $3.90 per issue Learn more Rent or buy this article Prices vary by article type from $1.95 to $39.95 Learn more Prices may be subject to local taxes which are calculated during checkout Author information Author notes These authors contributed equally: Qian Xu, Yichen Nie Authors and Affiliations Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA Qian Xu, Yichen Nie, Ronghua Zhang, Jeremiah A. Johnson & Alison E. Wendlandt State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry, Nanjing University, Nanjing, China Qian Xu Stratingh Institute for Chemistry, University of Groningen, Groningen, The Netherlands Jacob-Jan Haaksma Small Molecule Drug Discovery, Bristol Myers Squibb, Cambridge, MA, USA Natalie Holmberg-Douglas, Farid van der Mei & Chloe Williams Actithera, Cambridge, MA, USA Paul M. Scola Authors Qian Xu View author publications Search author on: PubMed Google Scholar Yichen Nie View author publications Search author on: PubMed Google Scholar Jacob-Jan Haaksma View author publications Search author on: PubMed Google Scholar Ronghua Zhang View author publications Search author on: PubMed Google Scholar Natalie Holmberg-Douglas View author publications Search author on: PubMed Google Scholar Farid van der Mei View author publications Search author on: PubMed Google Scholar Paul M. Scola View author publications Search author on: PubMed Google Scholar Chloe Williams View author publications Search author on: PubMed Google Scholar Jeremiah A. Johnson View author publications Search author on: PubMed Google Scholar Alison E. Wendlandt View author publications Search author on: PubMed Google Scholar Corresponding author Correspondence to Alison E. Wendlandt . Supplementary information Supplementary Information This Supplementary Information file contains the following sections: 1. General experimental methods; 2. Materials and reagents; 3. Instrumentation; 4. Reaction condition optimization; 5. Substrate synthesis; 6.Mechanistic studies; 7. Comparison between our migration method vs previous route in the preparation of the sclareolide derivative; 8.O-Mapping data acquisition; 9. Chiral HPLC separation; 10. X-ray data collection and refinement; 11. Computational Details; 12. NMR spectrums; and 13. References. Peer Review File Rights and permissions Reprints and permissions About this article Cite this article Xu, Q., Nie, Y., Haaksma, JJ. et al. Alcohol group migration by proximity-enhanced H atom abstraction. Nature (2026). https://doi.org/10.1038/s41586-026-10347-4 Download citation Received : 16 October 2025 Accepted : 02 March 2026 Published : 10 March 2026 DOI : https://doi.org/10.1038/s41586-026-10347-4 Share this article Anyone you share the following link with will be able to read this content: Get shareable link Sorry, a shareable link is not currently available for this article. Copy shareable link to clipboard Provided by the Springer Nature SharedIt content-sharing initiative