Convenient access to 5-membered cyclic iminium ions: evidence for a stepwise [4 + 2] cycloaddition mechanism

Org Biomol Chem. 2019 Mar 6;17(10):2705-2714. doi: 10.1039/c9ob00262f.


In situ generation and reaction of novel 5-membered N-tosyl cyclic α,β-unsaturated iminium ions from readily prepared stable precursors is demonstrated. Formal iminium Diels-Alder cycloaddition proceeded in good yield via a stepwise rather than concerted cycloaddition process, confirmed through the isolation of a Mukaiyama-Michael type intermediate. Relative stereochemistry was determined upon subsequent intramolecular cyclisation under Lewis acid catalysis to afford formal endo 5,6-spirobicyclic adducts, as confirmed by crystallography. Further synthetic elaboration towards complex molecular scaffolds based on the dinoflagellate metabolite portimine, a potent apoptosis inducer, were also developed.

Publication types

  • Research Support, Non-U.S. Gov't