Special Issue "Recent Developments on Catalysis by Metalloporphyrins and Analogues"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: 15 December 2019

Special Issue Editors

Guest Editor
Dr. Mário Manuel Quialheiro Simões

Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Website | E-Mail
Interests: organic chemistry; sustainable chemistry; oxidation; metalloporphyrins; catalysis; homogeneous catalysis; heterogeneous catalysis
Guest Editor
Dr. Susana Luísa Henriques Rebelo

Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Campo Alegre Street, 4169-007 Porto, Portugal
Website | E-Mail
Interests: metalloporphyrins; catalysis; oxidation; green chemistry; hydrogen peroxide; materials science; mechanisms

Special Issue Information

Dear Colleagues,

The synthetic versatility and the potential applications of metalloporphyrins in several fields, including catalysis, have catapulted the interest of researchers in these complexes, all over the world, particularly trying to mimic biological systems, such as cytochrome P450 enzymes. In the last few decades, significant developments on catalytic processes based on synthetic metalloporphyrins have been registered, mostly devoted to, although not exclusively to, oxidative transformations. In addition to hydroxylation, epoxidation or sulfoxidation reactions, other metalloporphyrins’ catalyzed transformations are playing an important role, such as reduction, halogenations or carbene transfer reactions, including significant developments on asymmetric catalysis. Meanwhile, several metalloporphyrin analogues are also playing a major role in catalysis.

We would like to invite authors to submit regular research papers, communications, and short reviews to this Special Issue, which aims to cover the most recent advances in the field of catalysis mediated by metalloporphyrins and analogues in either homogeneous and heterogeneous conditions, including asymmetric catalytic systems.

Dr. Mário Manuel Quialheiro Simões
Dr. Susana Luísa Henriques Rebelo
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Porphyrins
  • Corroles
  • Phthalocyanines
  • Catalysis
  • Biomimetic catalysis
  • Homogeneous catalysis
  • Heterogeneous catalysis

Published Papers (2 papers)

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Research

Open AccessArticle
Studies of the Catalytic Activity of Iron (III) Porphyrins for the Protection of Carbonyl Groups in Homogeneous Media
Catalysts 2019, 9(4), 334; https://doi.org/10.3390/catal9040334
Received: 8 March 2019 / Revised: 29 March 2019 / Accepted: 31 March 2019 / Published: 4 April 2019
PDF Full-text (9095 KB) | HTML Full-text | XML Full-text | Supplementary Files
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Figures

Graphical abstract

Open AccessArticle
Tin(IV)-Porphyrin Tetracarbonyl Cobaltate: An Efficient Catalyst for the Carbonylation of Epoxides
Catalysts 2019, 9(4), 311; https://doi.org/10.3390/catal9040311
Received: 4 March 2019 / Revised: 23 March 2019 / Accepted: 27 March 2019 / Published: 29 March 2019
PDF Full-text (1479 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Cationic tin(IV) porphyrins with tetracarbonyl cobaltates were synthesized, exhibiting bifunctional catalytic reactivity. The Lewis acidic tin-porphyrin center activated epoxides; concurrently, cobalt carbonyl anions efficiently opened epoxides and delivered carbonyl moieties. Thus, a series of β-lactones with a high synthetic value were obtained. This [...] Read more.
Cationic tin(IV) porphyrins with tetracarbonyl cobaltates were synthesized, exhibiting bifunctional catalytic reactivity. The Lewis acidic tin-porphyrin center activated epoxides; concurrently, cobalt carbonyl anions efficiently opened epoxides and delivered carbonyl moieties. Thus, a series of β-lactones with a high synthetic value were obtained. This catalytic system showed excellent efficiency exceeding a turnover number of one thousand with a broad substrate scope. In addition, the presented tin porphyrin-based catalyst exhibited exclusive chemoselectivity to terminal epoxides over internal ones. The selective carbonylation of di-epoxides demonstrated the usefulness of these catalysts in the synthesis of complex molecular structures. Full article
(This article belongs to the Special Issue Recent Developments on Catalysis by Metalloporphyrins and Analogues)
Figures

Scheme 1

Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Cyclopropanation Reactions Catalyzed by Metalloporphyrins Bound to Gold Nanoparticles
Author: Pietro Tagliatesta
Affiliation: Dipartimento di Chimica, Università degli Studi di Roma “Tor Vergata”, Rome, Italy
Correspondence: [email protected]

Title: Direct and Multiple Functionalization of the Benzofuran Core by Mn(III)porphyrin Catalytic Oxidation
Authors: Craig John Medforth
Affiliations: Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal
Correspondence: [email protected]

Title: Acetalization of carbonyl compounds catalyzed by ironporphyrins
Authors: Gabriel Kaetan Baio Ferreira, Charles Carvalho, Shirley Nakagaki*
Affiliations: Laboratório de Bioinorgânica e Catálise, Departamento de Química - Centro Politécnico, Universidade Federal do Paraná (UFPR), Curitiba – PR, Brazil
Correspondence: [email protected]
Abstract: Protection of carbonyl groups giving acetal products is a key reaction in fine chemistry due to the high reactivity of aldehydes and ketones in certain media and this processes may 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 additional coordination of substrates. In this way we selected three iron(III)porphyrins to be tested as catalysts towards acetalization of benzaldehyde with ethanol and triethyl orthoformate (TEOF) in homogeneous phase: [tetraphenylporphyrin iron(III)], [tetra(2,6-difluorphenyl)porphyrin iron(III)] and [tetra(2,3,4,5,6-pentafluorphenyl)porphyrin iron (III)]. The full fluorinated complex showed the highest catalytic activity and kinetic parameters were evaluated for this reaction, exhibiting an increasing in the rate of the reaction of 551-fold in comparison to the non-catalyzed reaction. The reaction scope was also investigated and the catalyst was active for the acetalization of benzaldehyde and acetophenone with different protective groups, such as alcohols, glycols, glycerol and epoxide, presenting selectivity for the protection of aldehyde with ethylene- and propyleneglycol giving cyclic acetals–up to 99% of conversion in 30 min at 40 ºC with no solvent.


 

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