π‐radical cascade to a chiral saddle‐shaped peropyrene : = [Pi]-radical cascade to a chiral saddle‐shaped peropyrene

Abstract: Reactions of open-shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π-magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via formation of multiple bonds and rings in a single step. Here, we explore the feasibility of using this “undesired” reaction of phenalenyl to build up strain and provide access to non-planar polycyclic aromatic hydrocarbons. To this end, we designed and synthesized a biradical system with two phenalenyl units linked via a biphenylene backbone. The design facilitates an intramolecular cascade reaction to a helically twisted saddle-shaped product, where the key transformations—ring-closure and ring-fusion—occur within one reaction. The negative curvature of the final peropyrene product, induced by the formed eight-membered ring, was confirmed by single-crystal X-ray diffraction analysis and the helical twist was validated via resolution of the product's enantiomers that display circularly polarized luminescence and high configurational stability

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• Alternative title: [Pi]-radical cascade to a chiral saddle‐shaped peropyrene
• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch
• Notes: Angewandte Chemie. - 136, 14 (2024) , e202318254, ISSN: 1521-3757

Contributors, Places and Time

• Event: Veröffentlichung
• (where): Freiburg
• (who): Universität
• (when): 2024
• Creator: Bernhardt, Annika ; Čavlović, Daniel ; Mayländer, Maximilian ; Blacque, Olivier ; Cruz, Carlos M. ; Richert, Sabine ; Juríček, Michal

Further information

• DOI: 10.1002/ange.202318254
• URN: urn:nbn:de:bsz:25-freidok-2580774
• Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.