104322-39-6Relevant articles and documents
Biologically Inspired and Magnetically Recoverable Copper Porphyrinic Catalysts: A Greener Approach for Oxidation of Hydrocarbons with Molecular Oxygen
Henriques, César A.,Fernandes, Auguste,Rossi, Liane M.,Ribeiro, M. Filipa,Calvete, Mário J. F.,Pereira, Mariette M.
, p. 3359 - 3368 (2016)
An efficient synthetic method for magnetically recoverable hybrid copper porphyrinic nanomaterials is reported. These functionalized magnetic materials prove to be efficient bioinspired oxidation catalysts of olefins and thiols, using molecular oxygen as oxidant, in total absence of reductants and solvents, with the highest TON (turnover number) yet achieved for this reaction (≈200 000). A comparative study between homogeneous and heterogeneous oxidation of cyclohexene is discussed, revealing the heterogeneous system to be the most promising concerning stability and reusability of the catalysts. The full characterization of the magnetic hybrid porphyrinic nanomaterials, by transmission electron microscopy, flame atomic absorption spectrometry, thermogravimetry, N2 sorption, and infrared spectroscopy, is also described.
Ecofriendly Porphyrin Synthesis by using Water under Microwave Irradiation
Henriques, César A.,Pinto, Sara M.A.,Aquino, Gilberto L.B.,Pineiro,Calvete, Mário J.F.,Pereira, Mariette M.
, p. 2821 - 2824 (2014)
Water, under microwave irradiation and at a temperature of 473 K, reaches pressures above 16 bar, being capable to act as catalyst, without the use of organic solvents and oxidants, for meso-substituted porphyrin synthesis. Sustainability of the reaction is proved by E Factor=35 and EcoScale value of 50.5, the highest so far obtained for porphyrin synthesis. Methodology's wide versatility is clearly demonstrated by the good yields obtained for both aryl and alkyl substituted porphyrins. These reaction conditions represent a huge development, not only by using very high concentrations, minimizing organic solvent usage, but also by eradicating toxic expensive solvents and oxidants.
Halogenated meso-phenyl Mn(III) porphyrins as highly efficient catalysts for the synthesis of polycarbonates and cyclic carbonates using carbon dioxide and epoxides
Cuesta-Aluja, Laia,Castilla, Javier,Masdeu-Bultó, Anna M.,Henriques, César A.,Calvete, Mário J.F.,Pereira, Mariette M.
, p. 489 - 494 (2016)
Introduction of halogen electron withdrawing atoms (chloro and fluoro) in the ortho position of the aryl groups of meso-tetraphenylporphyrin manganese(III) complexes increased their activity as catalysts in the reaction of carbon dioxide with epoxides, wh
Bioinspired-metalloporphyrin magnetic nanocomposite as a reusable catalyst for synthesis of diastereomeric (-)-isopulegol epoxide: Anticancer activity against human osteosarcoma cells (MG-63)
Dias, Lucas D.,De Carvalho, Ana L. M. Batista,Pinto, Sara M. A.,Aquino, Gilberto L. B.,Calvete, Mário J. F.,Rossi, Liane M.,Marques,Pereira, Mariette M.
, (2019)
In the present study, we developed a green epoxidation approach for the synthesis of the diastereomers of (-)-isopulegol benzyl ether epoxide using molecular oxygen as the oxidant and a hybrid manganese(III)-porphyrin magnetic reusable nanocomposite as th
Rate-Limiting Step of Epoxidation Reaction of the Oxoiron(IV) Porphyrin π-Cation Radical Complex: Electron Transfer Coupled Bond Formation Mechanism
Fujii, Hiroshi,Hada, Masahiko,Ishimizu, Yuri,Ma, Zhifeng
, p. 17687 - 17698 (2021/12/01)
Epoxidation reactions catalyzed by high-valent metal-oxo species are key reactions in various biological and chemical processes. Because the redox potentials of alkenes are higher than those of most high-valent metal-oxo species, the electron transfer (ET
Structure and dynamics processes in free-base chlorins controlled by chemical modifications of macroring and aryl groups in: Meso -positions
?niechowska,Paluch,Potrzebowski
, p. 24795 - 24805 (2017/07/11)
In this work we present the synthesis, detailed structural characterization and analysis of molecular motion for unsymmetrical pyrrolidine-fused chlorins employing NMR, UV spectroscopy and DFT theoretical calculations. In samples, the meso-rings were modified by substitution of hydrogen by fluorine in ortho1 and meta positions 2. The sample with perfluorinated ring 3 and phenyl derivative 4 were used as reference species. The assignment of signals was performed employing 2D NMR techniques. The rotational dynamics was examined by means of 1H and 19F variable-temperature (VT) 1D NMR spectroscopy and 2D EXSY experiments. The synergism of steric effect between pyrrolidine ring and meso-rings is unambiguously proved. Models 1 and 3 behave very similar, aromatic rings are rigid in temperature range 233-373 K. For sample 2 and 4 the distinct molecular dynamics was revealed. The barrier of rotation depends on localization of ring in the chlorin structure. Those which are bonded in the neighborhood of pyrrolidine ring are more rigid compared to those localized on the opposite site. The temperature is a trigger which sequentially releases the rotation of aromatic group in the desired localization. Introduction of fluorine in labeled position has influence on static geometry defined by saddling angles.
