Unexpected one-pot formation of 1H-6a,8a-epiminotricyclopenta[a,c,e][8]annulene system from cyclopentanone, ammonia and dimethyl fumarate. Synthesis of highly strained polycyclic nitroxide and  EPR study

Submitting author affiliation:
NIOCH SB RAS, Novosibirsk, Russian Federation

Beilstein Arch. 2019, 201987. https://doi.org/10.3762/bxiv.2019.87.v1

Published 20 Aug 2019



The unexpected formation of a highly strained polycyclic amine was found in a one-pot synthesis from cyclopentanone, dimethylfumarate and ammonium acetate. This multistep reaction includes 1,3-dipolar cycloaddition of dimethyl fumarate to the cyclic azomethine ylide formed in situ from cyclopentanone and ammonia. The polycyclic amine product was easily converted into a sterically-shielded polycyclic nitroxide. The EPR spectra and spin relaxation behavior of the nitroxide was studied in solution.  The spin relaxation seems well suited for use as a biological spin label and are comparable with those of cyclic nitroxides with two spirocyclic moieties adjacent to N-O• group.

Keywords: Domino reaction, azomethine ylide, nitroxide

Supporting Information

Format: DOC Size: 511.5 KB   Download

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:

Dobrynin, S.; Kirilyuk, I.; Gatilov, Y.; Kuzhelev, A.; Krumkacheva, O.; Fedin, M.; Bowman, M.; Bagryanskaya, E. Beilstein Arch. 2019, 201987. doi:10.3762/bxiv.2019.87.v1

Download citation
Download RIS (Reference Manager) Download BIB (BIBTEX)

© 2019 Dobrynin et al.; licensee Beilstein-Institut.
This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the authors and source are credited.
The license is subject to the Beilstein Archives terms and conditions: (https://www.beilstein-archives.org/xiv/terms)