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Catalysts 2019, 9(4), 334; https://doi.org/10.3390/catal9040334

Studies of the Catalytic Activity of Iron (III) Porphyrins for the Protection of Carbonyl Groups in Homogeneous Media

Laboratório de Bioinorgânica e Catálise, Departamento de Química—Centro Politécnico, Universidade Federal do Paraná (UFPR), Curitiba PR 81531980, Brazil
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Received: 8 March 2019 / Revised: 29 March 2019 / Accepted: 31 March 2019 / Published: 4 April 2019
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
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Abstract

The protection of carbonyl groups that produce acetal products is a key reaction in fine chemistry due to the high reactivity of aldehydes and ketones in certain media. This process can be catalyzed by protic or Lewis acids. Since metalloporphyrins often possess free axial positions in the central metal, they can be applied as Lewis acid catalysts, allowing the additional coordination of substrates. Therefore, three ferric complexes were selected to be evaluated as catalysts for the acetalization of benzaldehyde with ethanol and triethyl orthoformate (TEOF) in the homogeneous phase: (i) 5,10,15,20-tetrakis(phenylporphyrin) iron (III) chloride (Fe0F); (ii) 5,10,15,20-tetrakis(2,6-difluorphenylporphyrin) iron (III) chloride (Fe2F); and (iii) 5,10,15,20-tetrakis(pentafluorphenylporphyrin) iron (III) chloride (Fe5F). The complex Fe5F showed the highest catalytic activity, and kinetic parameters were evaluated for this reaction, exhibiting an increasing rate of reaction of about 550-fold in comparison with the non-catalyzed reaction. The reaction scope was also investigated, and Fe5F was found to be active for the acetalization of benzaldehyde and acetophenone, with different protective agents such as alcohols, glycols, glycerol, and epoxide being selective for the formation of cyclic acetals. The protection of benzaldehyde with ethylene glycol and propylene glycol were also studied at different temperatures, and turnover frequency (TOF) values of up to 360 h−1 were determined at 40 °C in homogenous media without the need for solvent or drying agents. View Full-Text
Keywords: porphyrin; acetalization; homogeneous catalysis; Lewis acid catalysis porphyrin; acetalization; homogeneous catalysis; Lewis acid catalysis
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Ferreira, G.K.B.; Carvalho, C.; Nakagaki, S. Studies of the Catalytic Activity of Iron (III) Porphyrins for the Protection of Carbonyl Groups in Homogeneous Media. Catalysts 2019, 9, 334.

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