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Investigation of the Scope of a New Route to ABCD-Bilanes and ABCD-Porphyrins

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journal contribution
posted on 05.09.2008 by Dilek Kiper Dogutan, Jonathan S. Lindsey
A new route to bilanes and porphyrins bearing four distinct meso substituents has been studied to elucidate the scope and gain entry to previously inaccessible compounds. The route entails (i) synthesis of a 1-bromo-19-acylbilane by acid-catalyzed condensation of a 1-acyldipyrromethane and a 9-bromodipyrromethane-1-carbinol and (ii) intramolecular cyclization of the 1-bromo-19-acylbilane in the presence of a metal salt (MgBr2, 3 mol equiv) and a non-nucleophilic base (DBU, 10 mol equiv) in a noncoordinating solvent (toluene) at 115 °C exposed to air to afford the corresponding magnesium(II) porphyrin. In this study, two sets of bilanes were initially prepared to explore substituent effects. In the first set, all bilanes vary only in the nature of the substituent at the 10-position. In the second set, all bilanes vary only in the nature of the substituent attached to the acyl unit (the 20-position). The substituents examined at the 10- and 20-positions include alkyl, aryl (electron-rich, electron-deficient, hindered), heteroaryl, ester, or no substituent (−H). The bilanes were obtained in 35−87% yield, and the target porphyrins in up to 60% yield. Further study of the scope focused on bilanes and porphyrins bearing three heterocyclic substituents (o-, m-, p-pyridyl) or four alkyl groups (ethyl, propyl, butyl, pentyl), in which case microwave irradiation was used for the porphyrin-forming step. Altogether, 17 bilanes and 19 porphyrins were prepared and characterized. In summary, the new route provides access to meso-substituted bilanes and porphyrins for which access is limited via other methods.