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Hexafluorophosphate-Triggered Hydrogen Isotope Exchange (HIE) in Fluorinated Environments: A Platform for the Deuteration of Aromatic Compounds via Strong Bond Activation

Title: Hexafluorophosphate-Triggered Hydrogen Isotope Exchange (HIE) in Fluorinated Environments: A Platform for the Deuteration of Aromatic Compounds via Strong Bond Activation
Authors: Ni, Yang; Lebelt, Jonathan; Barp, Milena; Kreuter, Florian; Buttkus, Hannah; Jin, Jiaye; Kretzschmar, Martin; Tonner-Zech, Ralf; Asmis, Knut R.; Gulder, Tanja
Publisher Information: Saarländische Universitäts- und Landesbibliothek
Publication Year: 2024
Collection: SciDok - Der Wissenschaftsserver der UdS (Universität des Saarlandes)
Subject Terms: ddc:500; deuterium; 1,1,1,3,3,3-hexafluoroisopropanol; ion vibrational spectroscopy; computational chemistry; hydrogen bonding cluster
Description: There is a perpetual need for efficient and mild methods to integrate deuterium atoms into carbon frameworks through late-stage modifications. We have developed a simple and highly effective synthetic route for hydrogen isotope exchange (HIE) in aromatic compounds under ambient conditions. This method utilizes catalytic amounts of hexafluorophosphate (PF6 ) in deuterated 1,1,1,3,3,3-hexafluoroisopropanol (HFIPd1) and D2O. Phenols, anilines, anisoles, and heterocyclic compounds were converted with high yields and excellent deuterium incorporations, which allows for the synthesis of a wide range of deuterated aromatic compounds. Spectroscopic and theoretical studies show that an interactive H-bonding network triggered by HFIP-d1 activates the typically inert P F bond in PF6 for D2O addition. The thus in situ formed DPO2F2 then triggers HIE, offering a new way to deuterated building blocks, drugs, and natural-product derivatives with high deuterium incorporation via the activation of strong bonds.
Document Type: article in journal/newspaper
Language: English
Relation: https://onlinelibrary.wiley.com/action/downloadSupplement?doi=10.1002%2Fanie.202417889&file=anie202417889-sup-0001-misc_information.pdf; hdl:20.500.11880/39744
DOI: 10.22028/D291-44535
DOI: 10.1002/anie.202417889
Availability: http://nbn-resolving.org/urn:nbn:de:bsz:291--ds-445351; https://doi.org/10.22028/D291-44535; https://doi.org/10.1002/anie.202417889
Rights: openAccess ; Attribution-NonCommercial-NoDerivatives 4.0 International CC BY-NC-ND 4.0 Deed ; https://creativecommons.org/licenses/by-nc-nd/4.0/
Accession Number: edsbas.CB13C2A8
Database: BASE