This work reports a biomimetic synthesis of polyarylated fluorene derivatives. The molecules are formed via intramolecular electrophilic aromatic substitution, resembling a cyclization leading towards the natural selaginpulvilins from selaginellins. The scope of the reaction was investigated, and the products were obtained in 60-95 % yields. Some of the compounds decompose to a stable radical. We investigated the nature and the origin of the radical using experimental methods, including EPR or electrochemical measurements, as well as theoretical methods, such as DFT calculations. Based on our observations, we hypothesize, that phenoxy radicals are formed in the first instance, which however undergo internal rearrangement to thermodynamically more stable carbon-centered radicals. The preliminary data also show the cytotoxic properties of some of the molecules.

Department of Analytical Chemistry Faculty of Science Charles University Hlavova 8 128 00 Prague Czech Republic

Department of Inorganic Chemistry Faculty of Science Charles University Hlavova 8 128 00 Prague Czech Republic

Department of Molecular Biology and Genetics Faculty of Arts and Science Canakkale Onsekiz Mart University Canakkale 17020 Turkey

Department of Organic Chemistry Center for Physical Sciences and Technology Akademijos g 7 Vilnius 08412 Lithuania

Department of Organic Chemistry Faculty of Science Charles University Hlavova 8 128 00 Prague Czech Republic

Institute of Organic Chemistry and Biochemistry Academy of Science of the Czech Republic Flemingovo nám 2 166 10 Prague Czech Republic

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Synthesis of Selaginpulvilin D by [2 + 2 + 2] Cyclotrimerization─A Second-Generation Approach