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Catalysts
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Catalysis in Heterocyclic and Organometallic Synthesis II
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Catalysis in Heterocyclic and Organometallic Synthesis II

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalysis in Organic and Polymer Chemistry".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 16515

Special Issue Editors

Prof. Dr. Antal Csampai

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Guest Editor
Institute of Chemistry, Faculty of Science, Eötvös Loránd University (ELTE), Pázmány Péter sétány 1/A, 1117 Budapest, Hungary
Interests: heterocyclic chemistry; organometallic chemistry of transition metals; NMR spectroscopy; stereochemistry; reaction mechanism; molecular modeling; antiproliferative compounds; cross coupling reactions; organocatalysis
Special Issues, Collections and Topics in MDPI journals
Dr. Tamás Jernei

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Guest Editor
Department of Biochemistry, Eötvös Loránd University, Pázmány Péter sétány 1/c, 1117 Budapest, Hungary
Interests: organic chemistry; synthetic chemistry; transition metal catalysis; medicinal chemistry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

In recent decades, diverse methods of catalysis, including transition metal catalysis, organocatalysis, their homogenous and heterogenous versions, as well as biocatalysis, have witnessed an extremely rapid development in a variety of chemical transformations utilized in the chemical, fuel, pharmaceutical and agricultural industries to afford a wide range of products having an impact on daily life. As a result of intensive research, a number of well-established concepts and tools are now available to obtain a deeper insight into the mechanisms of catalytic reactions allowing to develop more and more sophisticated catalytic systems and conditions capable of governing the elementary steps of a multistep transformation to proceed via a rationally designed pathway. Although in the chemistry of heterocyclic and organometallic compounds, representing two large and partly overlapping domains of chemical research, the most efficient, robust, and often environmentally benign synthetic strategies are based on catalysis, there is a constant need to develop further superior systems of higher catalytic activity and specificity and to elaborate catalytic versions of extensively used stoichiometric organic syntheses with particular regards to asymmetric transformations. In addition to the elaboration and utilization of novel synthetic procedures, in the submitted papers, the structure–reactivity relationships and mechanism of catalytic transformations are also expected to be placed in particular focus, since for the development  and design of novel catalytic systems, there is a constant need to obtain deeper insight into catalytic processes.

Prof. Dr. Antal Csampai
Dr. Tamás Jernei
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 submissions that pass pre-check are 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 2700 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

  • Heterocyclic synthesis
  • Synthesis of organometallics
  • Metal catalysis
  • Organocatalysis
  • Biocatalysis
  • Chemoselective transformations
  • Asymmetric synthesis
  • Catalytic annulation reactions
  • Enantioselective syntheses
  • Reaction mechanism

Related Special Issues

Published Papers (9 papers)

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Research

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14 pages, 2878 KiB  
Communication
Comparison of Catalytic Properties of the Easily Interconvertible, Water-Soluble [RuHCl(CO)(mtppms-Na)3] and [RuH(H2O)(CO)(mtppms-Na)3][BF4]
by Henrietta Horváth, Gábor Papp, Ferenc Joó and Ágnes Kathó
Catalysts 2023, 13(1), 197; https://doi.org/10.3390/catal13010197 - 13 Jan 2023
Viewed by 1116
Abstract
The effect of the mobile interconversion of [RuHCl(CO)(mtppms-Na)3] 1, and [RuH(H2O)(CO)(mtppms-Na)3]+ 2, was studied in hydrogenation of phenylacetylene and cinnamaldehyde in aqueous–organic biphasic systems, as a function of the [...] Read more.
The effect of the mobile interconversion of [RuHCl(CO)(mtppms-Na)3] 1, and [RuH(H2O)(CO)(mtppms-Na)3]+ 2, was studied in hydrogenation of phenylacetylene and cinnamaldehyde in aqueous–organic biphasic systems, as a function of the chloride concentration and the pH of the aqueous phase. Catalytic activity of the two complexes was also determined in homogeneous organic solvents without any additives. In the biphasic system, the rate of selective hydrogenation of phenylacetylene to styrene was strongly increased upon addition of NaCl, while the reaction of cinnamaldehyde slowed, with no change in product distribution. Both reactions responded with a rate decrease upon increasing the pH of the aqueous phase. It was concluded that hydrogenation of phenylacetylene was catalyzed by 1 with no chloride dissociation, while in the reduction of cinnamaldehyde, the aquo-complex 2 was the active catalytic species. Catalytic cycles were suggested to rationalize these findings. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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9 pages, 2996 KiB  
Article
Self-Supported Polymeric Ruthenium Complexes as Olefin Metathesis Catalysts in Synthesis of Heterocyclic Compounds
by Adam A. Rajkiewicz, Anna Kajetanowicz and Karol Grela
Catalysts 2022, 12(10), 1087; https://doi.org/10.3390/catal12101087 - 21 Sep 2022
Cited by 2 | Viewed by 1427
Abstract
New ruthenium olefin metathesis catalysts containing N-heterocyclic carbene (NHC) connected by a linker tether to a benzylidene ligand were studied. Such obtained self-chelated Hoveyda–Grubbs type complexes existed in the form of an organometallic polymer but could still catalyze olefin metathesis after being dissolved [...] Read more.
New ruthenium olefin metathesis catalysts containing N-heterocyclic carbene (NHC) connected by a linker tether to a benzylidene ligand were studied. Such obtained self-chelated Hoveyda–Grubbs type complexes existed in the form of an organometallic polymer but could still catalyze olefin metathesis after being dissolved in an organic solvent. Although these polymeric catalysts exhibited a slightly lower activity compared to structurally related nonpolymeric catalysts, they were successfully used in a number of ring-closing metathesis reactions leading to a variety of heterocyclic compounds, including biologically and pharmacologically related analogues of cathepsin K inhibitor and sildenafil (Viagra™). In the last case, a good solubility of a polymeric catalyst in toluene allowed the separation of the product from the catalyst via simple filtration. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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15 pages, 3335 KiB  
Article
Pd-Catalyzed Hirao P–C Coupling Reactions with Dihalogenobenzenes without the Usual P-Ligands under MW Conditions
by Bianka Huszár, Petra Regina Varga, Nóra Á. Szűcs, András Simon, László Drahos and György Keglevich
Catalysts 2022, 12(10), 1080; https://doi.org/10.3390/catal12101080 - 20 Sep 2022
Cited by 2 | Viewed by 1282
Abstract
A literature survey of the P–C coupling reactions of 1,4-and 1,2-bromo-iodobenzenes with diphenylphosphine oxide or diethyl phosphite under different conditions comprising Pd-, Ni-, or Cu-catalysis revealed that, depending on the experimental details, the yields of the corresponding >P(O)-bromobenzenes were rather diverse and occasionally [...] Read more.
A literature survey of the P–C coupling reactions of 1,4-and 1,2-bromo-iodobenzenes with diphenylphosphine oxide or diethyl phosphite under different conditions comprising Pd-, Ni-, or Cu-catalysis revealed that, depending on the experimental details, the yields of the corresponding >P(O)-bromobenzenes were rather diverse and occasionally contradicting. Therefore, the reactivity of a series of 1,4-, 1,3- and 1,2-dibromo- and bromo-iodobenzenes with the above mentioned P-reagents was evaluated under the “P-ligand-free” microwave (MW)-assisted conditions elaborated by us. Starting from dibromobenzenes and iodo-bromoarenes, practical and competent syntheses were developed for phosphonoyl- and phosphinoyl-bromoarenes, and, in a few instances, for arenes with two P-functions. The cheaper dibromobenzenes may be substituted for the bromo-iodo derivatives. In all, 12 products were prepared in yields of 45–82%. They were fully characterized. The method described does not require the use of traditional P-ligands. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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13 pages, 4363 KiB  
Article
β-Amino Acid Organocatalysts in the Asymmetric Michael Addition of Isobutyraldehyde to N-Substituted Maleimides
by Viktória Kozma, Zsolt Szakonyi and György Szőllősi
Catalysts 2022, 12(9), 992; https://doi.org/10.3390/catal12090992 - 02 Sep 2022
Cited by 1 | Viewed by 1286
Abstract
Asymmetric Michael additions of carbonyl compounds to N-substituted maleimides are among the most convenient reactions to prepare optically pure succinimide building blocks. Although a few β-amino acids were found to be highly efficient organocatalysts in the addition of α-branched aldehydes, the effect [...] Read more.
Asymmetric Michael additions of carbonyl compounds to N-substituted maleimides are among the most convenient reactions to prepare optically pure succinimide building blocks. Although a few β-amino acids were found to be highly efficient organocatalysts in the addition of α-branched aldehydes, the effect of their structure on the results of these reactions has not yet been investigated. In the present study, we disclose several unexpected and interesting structural effects of aliphatic and cycloaliphatic β-amino acids obtained in the enantioselective conjugate addition of isobutyraldehyde to N-benzylmaleimide. The dependence of the sense of the enantioselectivity on the bulkiness of the substituent on the β-carbon atom, the beneficial spatial arrangements of the functional groups in cis isomers with cyclohexane scaffold and the inversion of the enantioselectivity depending on the absence of a base additive observed with some trans isomers are unprecedented findings. The minor influence of the nitrogen substituent of the maleimide ring on both the reaction rate and the enantioselectivity was also evidenced using alicyclic β-amino acid prepared from an easily available terpene derivative. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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22 pages, 9462 KiB  
Article
Poisoning and Reuse of Supported Precious Metal Catalysts in the Hydrogenation of N-Heterocycles, Part II: Hydrogenation of 1-Methylpyrrole over Rhodium
by László Hegedűs, Tien Thuy Thanh Nguyen, Krisztina Lévay, Krisztina László, György Sáfrán and Andrea Beck
Catalysts 2022, 12(7), 730; https://doi.org/10.3390/catal12070730 - 01 Jul 2022
Cited by 2 | Viewed by 2168
Abstract
Poisoning effect of nitrogen on heterogeneous, supported precious metal catalysts, along with their recycling, was further examined in the liquid-phase hydrogenation of 1-methylpyrrole (MP) to 1-methylpyrrolidine (MPD) over rhodium on carbon or γ-alumina, in methanol, under non-acidic conditions, at [...] Read more.
Poisoning effect of nitrogen on heterogeneous, supported precious metal catalysts, along with their recycling, was further examined in the liquid-phase hydrogenation of 1-methylpyrrole (MP) to 1-methylpyrrolidine (MPD) over rhodium on carbon or γ-alumina, in methanol, under non-acidic conditions, at 25–50 °C and 10 bar. Reusing a spent, unregenerated 5% Rh/C or 5% Rh/γ-Al2O3 catalyst, it was found that the conversion of this model substrate and the activity of the catalyst were strongly dependent on the amount of catalyst, the type of support, the catalyst pre- or after-treatment, the temperature, and the number of recycling, respectively. An unexpected catalytic behaviour of rhodium was observed when it was used in a prehydrogenated form, because no complete conversion of MP was achieved over even the fresh Rh/C or Rh/γ-Al2O3, contrary to the untreated one. In addition, there was a significant difference in the reusability and activity of these rhodium catalysts, depending on their supports (activated carbon, γ-alumina). These diversions were elucidated by applying dispersion (O2- and H2-titration), temperature-programmed desorption of ammonia (NH3-TPD), and transmission electron microscopy (TEM) measurements. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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21 pages, 20591 KiB  
Article
Synthetic and DFT Modeling Studies on Suzuki–Miyaura Reactions of 4,5-Dibromo-2-methylpyridazin-3(2H)-one with Ferrocene Boronates, Accompanied by Hydrodebromination and a Novel Bridge-Forming Annulation In Vitro Cytotoxic Activity of the Ferrocenyl–Pyridazinone Products
by Nour-Eddine El Alaoui, Mohammed Boulhaoua, Dániel Hutai, Rita Oláh-Szabó, Szilvia Bősze, Ferenc Hudecz and Antal Csámpai
Catalysts 2022, 12(6), 578; https://doi.org/10.3390/catal12060578 - 24 May 2022
Viewed by 1787
Abstract
This paper presented the efficiency of different Pd-based catalytic systems in a series of SM reactions of 4,5-dibromo-2-methylpyridazin-3(2H)-one with ferroceneboronic acid, ferrocene-1,1′-diboronoc acid, and its bis-pinacol ester. In addition to the disubstituted product, these transformations afford substantial amounts of isomeric [...] Read more.
This paper presented the efficiency of different Pd-based catalytic systems in a series of SM reactions of 4,5-dibromo-2-methylpyridazin-3(2H)-one with ferroceneboronic acid, ferrocene-1,1′-diboronoc acid, and its bis-pinacol ester. In addition to the disubstituted product, these transformations afford substantial amounts of isomeric 4- and 5-ferrocenyl-2-methylpyridazin-3(2H)-ones, and a unique asymmetric bi-pyridazinone-bridged ferrocenophane with a screwed molecular architecture. The reactions of phenylboronic acid, conducted under the conditions, are proven to be the most reductive in the conversions of ferroceneboronic acid, and produce 2-methyl-4,5-diphenylpyridazin-3(2H)-one as single product, supporting our view about solvent-mediated hydrodehalogenations that are supposed to proceed via the assistance of the ferrocenyl group present in the reaction mixture, or attached to the bromo-pyridazinone scaffold, which is constructed in the first SM coupling of the heterocyclic precursor. A comparative DFT modelling study on the structures and possible transformations of relevant bromo-, ferrocene- and phenyl-containing carbopalladated intermediate pairs was carried out, providing reasonable mechanisms suitable to account for the apparently surprising regioselectivity of the alternative hydrodebromination processes, and for the formation of the ferrocenophane product. Supporting the results of DFT modelling studies, the implication of DMF as a hydrogen transfer agent in the hydrodebromination reactions is evidenced by deuterium labelling experiments using the solvent mixtures DMF-d7–H2O (4:1) and DMF–D2O (4:1). The organometallic products display antiproliferative effects on human malignant cell lines. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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10 pages, 16500 KiB  
Communication
Effect of Iodide on the pH-Controlled Hydrogenations of Diphenylacetylene and Cinnamaldehyde Catalyzed by Ru(II)-Sulfonated Triphenylphosphine Complexes in Aqueous–Organic Biphasic Systems
by Ágnes Kathó, Henrietta H. Horváth, Gábor Papp and Ferenc Joó
Catalysts 2022, 12(5), 518; https://doi.org/10.3390/catal12050518 - 05 May 2022
Cited by 2 | Viewed by 1654
Abstract
The effect of NaI on hydrogenation of diphenylacetylene catalyzed by the water-soluble [{RuCl(mtppms-Na)2}2(µ-Cl)2] (1) (mtppms-Na = meta-monosulfonated triphenylphosphine sodium salt) is reported. Hydrogenations were performed under mild conditions (P [...] Read more.
The effect of NaI on hydrogenation of diphenylacetylene catalyzed by the water-soluble [{RuCl(mtppms-Na)2}2(µ-Cl)2] (1) (mtppms-Na = meta-monosulfonated triphenylphosphine sodium salt) is reported. Hydrogenations were performed under mild conditions (P(H2) = 1 bar, T = 50–80 ℃) in aqueous–organic biphasic reaction mixtures wherein the catalyst was dissolved in aqueous phase of various pHs. In acidic solutions, addition of NaI to 1 + mtppms-Na increased the selective conversion of diphenylacetylene to stilbenes from 10% to 90% but did not effect the high Z-selectivity (up to 98%). In contrast, in basic solutions the major product was diphenylethane (up to 70%), and the yield of E-stilbene exceeded that of the Z-isomer. 1H and 31P NMR measurements revealed that depending on the absence or presence of NaI, the catalytically active Ru(II)-hydride species in acidic solutions was [RuHCl(mtppms-Na)3], 2, or [RuHI(mtppms-Na)3], 5, respectively, while in basic solutions, both 2 and 5 were hydrogenated further to yield the same hydride species, cis,fac-[RuH2(H2O)(mtppms-Na)3]. [RuHI(mtppms-Na)3] proved superior to [RuHCl(mtppms-Na)3] as a catalyst for the selective hydrogenation of cinnamaldehyde to dihydrocinamaldehyde. This finding was explained by a facile formation of a (putative) dihydrogen complex [Ru(H2)I2(H2O)(mtppms-Na)2] intermediate, resulting in fast heterolytic activation of H2. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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13 pages, 2878 KiB  
Article
Role of Lewis Acid Metal Centers in Metal–Organic Frameworks for Ultrafast Reduction of 4-Nitrophenol
by Jagannath Panda, Soumya Prakash Biswal, Himanshu Sekhar Jena, Arijit Mitra, Raghabendra Samantray and Rojalin Sahu
Catalysts 2022, 12(5), 494; https://doi.org/10.3390/catal12050494 - 29 Apr 2022
Cited by 5 | Viewed by 2564
Abstract
Metal–Organic Frameworks (MOFs) can be a good alternative to conventional catalysts because they are non-toxic and can be selective without compromising efficiency. Nano MOFs such as UiO-66 have proven themselves to be competitive in the catalytic family. In this study, we report the [...] Read more.
Metal–Organic Frameworks (MOFs) can be a good alternative to conventional catalysts because they are non-toxic and can be selective without compromising efficiency. Nano MOFs such as UiO-66 have proven themselves to be competitive in the catalytic family. In this study, we report the excellent catalytic behavior of UiO-66 MOF in the reduction of a model reaction: 4-Nitrophenol (4-NP) to 4-Aminophenol (4-AP) over MOF-5 (Zn-BDC) and MIL-101 (Fe-BDC). Nano UiO-66 crystals were synthesized by a hydrothermal process and characterized by Powder X-ray Diffraction, Diffused Reflectance UV-Vis spectroscopy, Scanning Electron Microscopy, and Transmission Electron Microscopy. The catalysts’ performance during the hydrogenation reduction reaction from 4-NP to 4-AP was investigated in the presence of a reducer, NaBH4. The UiO-66 nano crystals exhibited excellent catalytic behavior owing to its large surface area and Lewis acidic nature at the metal nodes. Furthermore, UiO-66 showed excellent recyclability behavior, verified during repeated consecutive use in a sequence. The catalyst yielded similar catalytic behavior during the reduction of nitrophenols at each cycle, which is a novel finding. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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Review

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21 pages, 11950 KiB  
Review
Masuda Borylation–Suzuki Coupling (MBSC) Sequence: A One-Pot Process to Access Complex (hetero)Biaryls
by Marco Kruppa and Thomas J. J. Müller
Catalysts 2023, 13(2), 350; https://doi.org/10.3390/catal13020350 - 04 Feb 2023
Cited by 4 | Viewed by 2306
Abstract
The direct formation of (hetero)biaryls from readily available (hetero)aryl halides under mild reaction conditions can be efficiently achieved through the Masuda borylation–Suzuki coupling (MBSC) sequence. The MBSC sequence catenates Pd-catalyzed Masuda borylation and Suzuki coupling into a one-pot process, giving access to diverse [...] Read more.
The direct formation of (hetero)biaryls from readily available (hetero)aryl halides under mild reaction conditions can be efficiently achieved through the Masuda borylation–Suzuki coupling (MBSC) sequence. The MBSC sequence catenates Pd-catalyzed Masuda borylation and Suzuki coupling into a one-pot process, giving access to diverse symmetrically and unsymmetrically substituted scaffolds. (Hetero)biaryls are ubiquitous structural motifs that appear in natural products, pharmaceutically relevant scaffolds, functional dyes, and several other structures. This review summarizes the development of the MBSC sequence and its improvements over the past two decades. Full article
(This article belongs to the Special Issue Catalysis in Heterocyclic and Organometallic Synthesis II)
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