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

  1. Sergey DobryninORCID Logo,
  2. Igor KirilyukORCID Logo,
  3. Yuri GatilovORCID Logo,
  4. Andrey KuzhelevORCID Logo,
  5. Olesya Krumkacheva,
  6. Matvey Fedin,
  7. Michael BowmanORCID Logo and
  8. Elena Bagryanskaya

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

  • Preprint


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

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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

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