Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's Purple

  1. Alexander StepakovORCID Logo,
  2. Alexander FilatovORCID Logo,
  3. Olesya Khoroshilova,
  4. Anna LarinaORCID Logo and
  5. Vitaly BoitsovORCID Logo

Submitting author affiliation: Saint-Petersburg State University, Saint-Petersburg, Russian Federation

Beilstein Arch. 2022, 20227. https://doi.org/10.3762/bxiv.2022.7.v1

Published 14 Feb 2022

  • Preprint

Abstract

A reliable method for the synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane through the 1,3-dipolar cycloaddition (1,3-DC) reactions of cyclopropenes to the stable azomethine ylide – protonated form of Ruhemann's Purple (PRP) has been developed. Both 3-substituted and 3,3-disubstituted cyclopropenes reacted with PRP, affording corresponding bis-spirocyclic 3-azabicyclo[3.1.0]hexane cycloadducts in moderate to good yields with high diastereofacial selectivity. Moreover, several unstable 1,2-disubstituted cyclopropenes were successfully trapped by the stable 1,3-dipole under mild conditions. The mechanism of cycloaddition reactions of cyclopropenes with PRP has been thoroughly studied using density functional theory (DFT) methods at the M11/cc-pVDZ level of theory. The cycloaddition reactions have been found to be HOMOcyclopropene – LUMOylide controlled while transition-state energies for the reaction of 3-methyl-3-phenylcyclopropene with PRP are fully consistent with the experimentally observed stereoselectivity.

Keywords: azomethine ylides, cycloaddition, cyclopropenes, DFT calculations, spiro heterocycles

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Stepakov, A.; Filatov, A.; Khoroshilova, O.; Larina, A.; Boitsov, V. Beilstein Arch. 2022, 20227. doi:10.3762/bxiv.2022.7.v1

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