Synthetic Metals 158 (2008) 796–801 Contents lists available at ScienceDirect Synthetic Metals journal homepage: www.elsevier.com/locate/synmet Design and electropolymerization of a new optically active iron tetraspirobifluorenyl porphyrin Cyril Poriel a , Yann Ferrand b , Paul Le Maux b , Jo ¨ elle Rault-Berthelot a,∗ ,G´ erard Simonneaux b a Universit´ e de Rennes 1, CNRS UMR 6226, Sciences Chimiques de Rennes, Mati` ere Condens´ ee et Syst` emes Electroactifs (MaCSE), Campus de Beaulieu, Bat. 10C, Avenue du G´ en´ eral Leclerc, 35042 Rennes Cedex, France b Universit´ e de Rennes 1, CNRS UMR 6226, Sciences Chimiques de Rennes, Ing´ enierie Chimique et Mol´ ecules pour le Vivant (ICMV), Campus de Beaulieu, Bat. 10C, Avenue du G´ en´ eral Leclerc, 35042 Rennes Cedex, France article info Article history: Received 27 November 2007 Accepted 14 May 2008 Available online 30 June 2008 Keywords: Anodic polymerization Chiral polymetalloporphyrins Spirobifluorene Iron-porphyrin Tetraarylporphyrin abstract The synthesis of optically active iron tetraspirobifluorenyl porphyrin is described. Organic conducting polymers have been prepared by anodic oxidation of these building blocks. Preliminary tests of asymmetric alkene epoxidation have been performed giving only moderate yields. © 2008 Elsevier B.V. All rights reserved. 1. Introduction Supporting transition metal catalytic complexes on conducting organic polymers have played an important role in the development of heterogeneous catalysts [1]. Thus, organometallic complexes with catalytic activity can be incorporated into polymers in a variety of methods, e.g., synthesis of a preformed polymer functionalized with a ligand, which is used to bind the metal, or synthesis of a monomer, which already contains the ligand–metal complex, fol- lowed by its polymerization. Numerous methods for immobilizing metalloporphyrins under insoluble materials have been reported [2] but very few under optically pure form [3–6] and even less with success for asymmetric reaction [5–7]. Connected with quater- nary carbon, spiro aromatic compounds are of more conformational rigidity than atropisomeric biaryl analogues, constituting a desir- able element in the design of chiral ligand for transition metal catalyzed asymmetric reactions. Although first synthesized in the 1930s and widely used today in organic optoelectronics [8], the significance of spirans such as spirobiindane [9,10], spirobifluorene [11], and spirobixanthene [12] in asymmetric catalysis has not been well recognized until recently. As the development of efficient chi- ral ligands is a central issue in the research field of asymmetric ∗ Corresponding author. Tel.: +33 223 235964; fax: +33 223 236732. E-mail address: Joelle.Rault@univ-rennes1.fr (J. Rault-Berthelot). catalysis, the high performance of these bulky and rigid ligands for numerous organic reactions appears to be extremely promis- ing. The spirobifluorene-porphyrins bearing four spirobifluorenyl groups in meso-position have been shown to exhibit good catalytic activities in oxidation reactions and also appear to be to be resis- tant to harsh catalytic conditions [13]. In this context, we reported in 2003 a new class of porphyrin polymers which can be used as heterogeneous catalysts [14]. The synthesis is based on the electro- chemical formation of a polyspirobifluorene film with porphyrin side chains. After being removed from the working electrode, this insoluble polymer has been used for olefin epoxidation or carbene transfer with excellent results. As an extension to our previous works, we now report, the synthesis of a new chiral metallopor- phyrin monomer (+)8 (Scheme 2) and its corresponding conducting polymer for asymmetric heterogeneous catalysis. 2. Result and discussion Here the synthetic strategy was based on the preparation of a chiral porphyrin ligand that might be polymerized by anodic oxidation. Usually a non-chiral and electropolymerizable group such as thiophene [15,16], fluorine [17], spirobifluorene [7] or vinyl group [18] is attached to the complex in order to allow the elec- tropolymerization process to occur. However, the chirality is usually not centered on these groups. For example, Schulz and coworkers recently designed new recyclable Cr-salen complexes [15,16] with 0379-6779/$ – see front matter © 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.synthmet.2008.05.003