resumo
New porphyrin indolin-2-one conjugates were synthesized via palladium-catalyzed amination reactions of iodinated and dibrominated indolin-2-one derivatives with (2-amino-5,10,15.20-tetraphenylpor phyrinato)nickel(II). The combination of palladium catalysts and the phosphine ligand dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) is an effective methodology for catalyzing the coupling of 5-iodo-, 5,7-dibromo- and 4,6-dibromo-1,3,3-trimethylindolin-2-one with 2-aminoporphyrin to give the corresponding mono-(2-aminoporphyrinyl)- and di-(2-aminoporphyrinyl)-substituted indolin-2-ones in satisfactory yields under mild conditions. The mono brominated porphyrinic derivatives also underwent cross-coupling reactions under similar catalytic conditions. The studies also demonstrated that the course of the coupling process depends on factors, such as the catalytic system, number and position of the halogen substituents and the heating condition. Insights into the reactivity trends of the 5-iodo; 4,6- and 5,7-dibrominated indolin-2-one derivatives was carried out using theoretical calculations performed using density-functional theory with the B3LYP functional. (C) 2012 Elsevier Ltd. All rights reserved.
palavras-chave
TOMENTOSA WILLD. DC; EFFICIENT SYNTHESIS; COUPLING REACTIONS; ARYL CHLORIDES; DERIVATIVES; TETRAPHENYLPORPHYRINS; DEHALOGENATION; INHIBITORS; BROMIDES; LIGANDS
categoria
Chemistry
autores
Menezes, JCJMDS; Pereira, AMVM; Neves, MGPMS; Silva, AMS; Santos, SM; Martinez, ST; Silva, BV; Pinto, AC; Cavaleiro, JAS
nossos autores
Sérgio Miguel Fernandes dos Santos
Investigador Auxiliaragradecimentos
Thanks are due to the University of Aveiro and also to FCT and FEDER for funding the QOPNA Research Unit (project PEst-C/QUI/UI0062/2011) and the Portuguese National NMR Network. J.C.J.M.D.S.M. thanks QOPNA for a research grant. A.M.V.M.P. and S.M.S. acknowledge FCT for post-doc fellowships (SFRH/BPD/64693/2009 and SFRH/BPD/64752/2009). CAPES, CNPq and FAPERJ are also acknowledged for financial support (S.T.M., B.V.S. and A.C.P.).