Florian Feist1,2,3,4,5, Sarah L Walden1,2, Jessica Alves1,2, Susanna V Kunz1,2, Aaron S Micallef1, Aidan J Brock1,2, John C McMurtrie1,2, Tanja Weil3, James P Blinco1,2, Christopher Barner-Kowollik1,2,4,5. 1. Centre for Materials Science, Queensland University of Technology (QUT), 2 George St., Brisbane, QLD, 4000, Australia. 2. School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George St., Brisbane, QLD, 4000, Australia. 3. Max Planck Institute for Polymer Research (MPIP), Ackermannweg 10, 55128, Mainz, Germany. 4. Macromolecular Architectures, Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131, Karlsruhe, Germany. 5. Institute of Nanotechnology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.
Abstract
Herein, we pioneer a wavelength-gated synthesis route to phenalene diimides. Consecutive Diels-Alder reactions of methylisophthalaldehydes and maleimides afford hexahydro-phenalene-1,6-diol diimides via 5-formyl-hexahydro-benzo[f]isoindoles as the intermediate. Both photoreactions are efficient (82-99 % yield) and exhibit excellent diastereoselectivity (62-98 % d.r.). The wavelength-gated nature of the stepwise reaction enables the modular construction of phenalene diimide scaffolds by choice of substrate and wavelength. Importantly, this synthetic methodology opens a facile avenue to a new class of persistent phenalenyl diimide neutral radicals, constituting a versatile route to spin-active molecules.
Herein, we pioneer a wavelength-gated synthesis route to phenalene diimides. Consecutive n class="Chemical">Diels-Alder reactions of methylisophthalaldehydes and maleimides afford hexahydro-phenalene-1,6-diol diimides via 5-formyl-hexahydro-benzo[f]isoindoles as the intermediate. Both photoreactions are efficient (82-99 % yield) and exhibit excellent diastereoselectivity (62-98 % d.r.). The wavelength-gated nature of the stepwise reaction enables the modular construction of phenalene diimide scaffolds by choice of substrate and wavelength. Importantly, this synthetic methodology opens a facile avenue to a new class of persistent phenalenyl diimide neutral radicals, constituting a versatile route to spin-active molecules.