Grant, Jacob A. and Lu, Zhou and Tucker, David E. and Hockin, Bryony M. and Yufit, Dmitry S. and Fox, Mark A. and Kataky, Ritu and Chechik, Victor and O'Donoghue, AnnMarie C. (2017) 'New Blatter-type radicals from a bench-stable carbene.', Nature communications., 8 . p. 15088.
Stable benzotriazinyl radicals (Blatter’s radicals) recently attracted considerable interest as building blocks for functional materials. The existing strategies to derivatize Blatter’s radicals are limited, however, and synthetic routes are complex. Here, we report that an inexpensive, commercially available, analytical reagent Nitron undergoes a previously unrecognized transformation in wet acetonitrile in the presence of air to yield a new Blatter-type radical with an amide group replacing a phenyl at the C(3)-position. This one-pot reaction of Nitron provides access to a range of previously inaccessible triazinyl radicals with excellent benchtop stabilities. Mechanistic investigation suggests that the reaction starts with a hydrolytic cleavage of the triazole ring followed by oxidative cyclization. Several derivatives of Nitron were prepared and converted into Blatter-type radicals to test the synthetic value of the new reaction. These results significantly expand the scope of using functionalized benzotriazinyls as stable radical building blocks.
|Full text:||(VoR) Version of Record|
Available under License - Creative Commons Attribution.
Download PDF (545Kb)
|Publisher Web site:||https://doi.org/10.1038/ncomms15088|
|Publisher statement:||This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/|
|Date accepted:||28 February 2017|
|Date deposited:||16 May 2017|
|Date of first online publication:||15 May 2017|
|Date first made open access:||16 May 2017|
Save or Share this output
|Look up in GoogleScholar|