Abstract

A series of bicyclic nitroxides, (3aR(S),6aR(S))-1-X-1,3,3-triethyloctahydropyrrolo[3,4-c]pyrrol-2-oxyls, where X = Et or t-Bu, have been prepared from the corresponding 3,4-disubstituted bis(hydroxymethyl)pyrrolidine-1-oxyls, which are among the most stable nitroxides known. The formation of this bicyclic system occurs upon in situ generation of trans-3-(aminomethyl)-4-(((methylsulfonyl)oxy)methyl)pyrrolidin-1-oxyls by various methods. Although the resulting nitroxides have highly strained trans-3,7-diazabicyclo[3.3.0]octane scaffold, they demonstrate high resistance to reduction with ascorbate (k₂ ~ 10^-3–10^-4 M^-1s^-1). A number of bicyclic conformationally rigid spin labels have been prepared.

Keywords: sterically shielded nitroxide, diazabicyclooctane, trans-fused 5,5-bicycles

Supporting Information

How to Cite

When a peer-reviewed version of this preprint is available, this information will be updated in the information box above. If no peer-reviewed version is available, please cite this preprint using the following information:

Usatov, M. S.; Zhurko, I. F.; Dobrynin, S. A.; Khoroshunova, Y. V.; Bagryanskaya, I. Y.; Rybalova, T. V.; Glazachev, Y. I.; Kirilyuk, I. A. Beilstein Arch. 2026, 202635. doi:10.3762/bxiv.2026.35.v1

Download Citation

Citation data can be downloaded as file using the "Download" button or used for copy/paste from the text window below.
Citation data in RIS format can be imported by all major citation management software, including EndNote, ProCite, RefWorks, and Zotero.