Sponsor
This work was funded by the National Science Foundation under grant no. 2247802 (DRS). The National Science Foundation provided funding for the BioAnalytical Mass Spectrometry Facility at PSU under grant no. 1828753. The National Science Foundation provided funding for the high-performance computing cluster at PSU under grant no. 1624776. The project described was supported, in part, by the Oregon State University Research Office. The content is solely the responsibility of the authors and does not necessarily represent the official views of the OSU Mass Spectrometry Center. The authors acknowledge the OSU Mass Spectrometry Center at Oregon State University and specific institutional instrument grants. Orbitrap Fusion Lumos – NIH #1S10OD020111-01, Waters Ion Mobility ToF Mass Spectrometer – NIH #1S10RR025628-01, Applied Biosystems 4000Qtrap – NIH #1S10RR022589-01, ABSciex Triple ToF 5600 – NIH #1S10RR027878-01.
Published In
Chemical Science
Document Type
Article
Publication Date
2-20-2025
Abstract
Arynes undergo a wide range of chemical transformations making them versatile reactive intermediates for organic synthesis. Access to arynes has long been dominated by pre-functionalised reagents, e.g., the venerable o-trimethylsilylaryl triflates. However, a move toward developing methods to access arynes that are both mild and efficient has prompted research into aryl “onium” aryne precursors. Here, we leverage aryl “onium” species as in situ or isolated intermediates in a net dehydrogenation of simple arenes as a novel and efficient way to access arynes. We describe a unified strategy in which two different tactics are employed to access diversely substituted arynes from simple arenes. (1) We developed a one-pot method that converts simple arenes into aryl thianthrenium salts and uses them in situ to generate arynes. (2) We developed a two-step process to convert arenes into aryl(Mes)iodonium salts and ultimately trapped arynes to expand the scope of compatible arenes. The net transformations from arenes to trapped arynes are complete with 2–4 hours. Mechanistic analysis through competition experiments, deuterium kinetic isotope effects (DKIE) and Density Functional Theory (DFT) provide key comparisons of the two approaches described in this work and yield a user's guide for selecting the appropriate “onium” leaving group based on the arene.
Rights
Copyright 2025 The Authors
Open Access Article.
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DOI
10.1039/d5sc00054h
Persistent Identifier
https://archives.pdx.edu/ds/psu/43140
Citation Details
Roberts, R. A., Metze, B. E., Javaly, N., McCormick, T. M., & Stuart, D. R. (2025). Access to arynes from arenes via net dehydrogenation: scope, synthetic applications and mechanistic analysis. Chemical Science.
