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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 (15 July 2020) | Viewed by 58500

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Prof. Dr. Nicola Della Ca’

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Department of Chemistry, Life Sciences and Environmental Sustainability (SCVSA), Parco Area delle Scienze 17/A, University of Parma, 43124 Parma, PR, Italy
Interests: catalytic sequential reactions for the synthesis of high value-added compounds from readily available reagents; transition metal-catalyzed C-H activation methodologies; carbonylation reactions; CO₂ activation chemistry
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Dear Colleagues,

Palladium is probably the most versatile and exploited transition metal in catalysis due to its capability to promote a myriad of organic transformations, both on laboratory and industrial scale. Both homogeneous and heterogeneous palladium-catalyzed reactions continue to play an essential role in organic synthesis. Natural alkaloids, bioactive compounds, pharmaceutical agents, agrochemicals, specialty polymers, etc., can be efficiently accessed by means of palladium catalysts. In general, palladium-based catalysts are involved in a variety of organic reactions, such as alkylation, arylation, cyclization, hydrogenation, oxidation, isomerization, cross-coupling, cascade, radical reactions, etc. Particular attention is devoted to the use of palladium catalysts in C-H bond activation, carbonylation, and asymmetric reactions or in combination with other metals. High chemo- regio- and diastereoselectivities as well as high levels of molecular sophistication can be achieved by employing tailored palladium-based catalytic systems under mild reaction conditions. However, despite these developments, every day new, exciting palladium-based applications are disclosed, giving renewed emphasis to palladium chemistry. Original research papers and reviews focusing on recent advancements in the field of palladium-catalyzed transformations are welcome for inclusion in this Special Issue of Catalysts.

Dr. Nicola Della Ca'
Guest Editor

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Keywords

Homogeneous and heterogeneous palladium catalysts
Pd-catalyzed cascade reactions
Pd-catalyzed cross-coupling reactions
Pd-catalyzed carbonylation reactions
Pd-catalyzed asymmetric reactions

Related Special Issue

Palladium-Catalyzed Reactions: Chapter II in Catalysts (2 articles)

Published Papers (14 papers)

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Editorial

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3 pages, 172 KiB

Open AccessEditorial

Palladium-Catalyzed Reactions

by Nicola Della Ca’

Catalysts 2021, 11(5), 588; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11050588 - 30 Apr 2021

Cited by 4 | Viewed by 2864

Abstract

Palladium is probably the most versatile and exploited transition metal in catalysis due to its capability to promote a myriad of organic transformations both at laboratory and industrial scales (alkylation, arylation, cyclization, hydrogenation, oxidation, isomerization, cross-coupling, cascade, radical reactions, etc [...] Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

Research

Jump to: Editorial, Review

10 pages, 2132 KiB

Open AccessArticle

Hydrotalcite-Supported Ag/Pd Bimetallic Nanoclusters Catalyzed Oxidation and One-Pot Aldol Reaction in Water

by Sangita Karanjit, Ayumu Tamura, Masaya Kashihara, Kazuki Ushiyama, Lok Kumar Shrestha, Katsuhiko Ariga, Atsushi Nakayama and Kosuke Namba

Catalysts 2020, 10(10), 1120; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10101120 - 29 Sep 2020

Cited by 6 | Viewed by 2897

Abstract

A highly active hydrotalcite-supported Ag/Pd bimetallic nanocluster catalyst has been developed by a simple, easy and safe chemical reduction method. The catalyst was characterized by high-resolution transmission electron microscopy (HR-TEM), which revealed very small (3.2 ± 0.7 nm) nanoclusters with a narrow size distribution. The bimetallic Ag/Pd catalyst showed strong cooperation between Ag and Pd for the alcohol oxidation reaction. The developed catalyst provided an efficient and environmentally friendly method for alcohol oxidation and one-pot cross-aldol condensation in water. A broad scope of α,β-unsaturated ketones with good to excellent yields were obtained under very mild conditions. This catalytic system offers an easy preparation method with a simple recovery process, good activity and reusability of up to five cycles without significant loss in the catalytic activity. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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29 pages, 6794 KiB

Open AccessArticle

Carbide-Modified Pd on ZrO₂ as Active Phase for CO₂-Reforming of Methane—A Model Phase Boundary Approach

by Norbert Köpfle, Kevin Ploner, Peter Lackner, Thomas Götsch, Christoph Thurner, Emilia Carbonio, Michael Hävecker, Axel Knop-Gericke, Lukas Schlicker, Andrew Doran, Delf Kober, Aleksander Gurlo, Marc Willinger, Simon Penner, Michael Schmid and Bernhard Klötzer

Catalysts 2020, 10(9), 1000; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10091000 - 02 Sep 2020

Cited by 13 | Viewed by 4068

Abstract

Starting from subsurface Zr⁰-doped “inverse” Pd and bulk-intermetallic Pd⁰Zr⁰ model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd⁰–ZrO₂ phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO₂ from bulk intermetallic Pd_xZr_y leads to a highly active composite layer of carbide-modified Pd⁰ metal nanoparticles in contact with tetragonal ZrO₂. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO₂ reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd⁰ toward CO at the Pd/ZrO₂ phase boundary, which serves the role of providing efficient CO₂ activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO₂ islands at the surface of a quasi-infinite Pd⁰ metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO₂–Pd⁰ state. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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21 pages, 3464 KiB

Open AccessArticle

Microkinetic Modeling of the Oxidation of Methane Over PdO Catalysts—Towards a Better Understanding of the Water Inhibition Effect

by Kevin Keller, Patrick Lott, Henning Stotz, Lubow Maier and Olaf Deutschmann

Catalysts 2020, 10(8), 922; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10080922 - 11 Aug 2020

Cited by 22 | Viewed by 3790

Abstract

Water, which is an intrinsic part of the exhaust gas of combustion engines, strongly inhibits the methane oxidation reaction over palladium oxide-based catalysts under lean conditions and leads to severe catalyst deactivation. In this combined experimental and modeling work, we approach this challenge with kinetic measurements in flow reactors and a microkinetic model, respectively. We propose a mechanism that takes the instantaneous impact of water on the noble metal particles into account. The dual site microkinetic model is based on the mean-field approximation and consists of 39 reversible surface reactions among 23 surface species, 15 related to Pd-sites, and eight associated with the oxide. A variable number of available catalytically active sites is used to describe light-off activity tests as well as spatially resolved concentration profiles. The total oxidation of methane is studied at atmospheric pressure, with space velocities of 160,000 h⁻¹ in the temperature range of 500–800 K for mixtures of methane in the presence of excess oxygen and up to 15% water, which are typical conditions occurring in the exhaust of lean-operated natural gas engines. The new approach presented is also of interest for modeling catalytic reactors showing a dynamic behavior of the catalytically active particles in general. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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10 pages, 8336 KiB

Open AccessArticle

Highly Crystallized Pd/Cu Nanoparticles on Activated Carbon: An Efficient Heterogeneous Catalyst for Sonogashira Cross-Coupling Reaction

by Zhen Wei, Zunyuan Xie, Lingxiang Gao, Yanyan Wang, Huaming Sun, Yajun Jian, Guofang Zhang, Liwen Xu, Jianming Yang, Weiqiang Zhang and Ziwei Gao

Catalysts 2020, 10(2), 192; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10020192 - 05 Feb 2020

Cited by 18 | Viewed by 2837

Abstract

In the quest for efficient and recyclable heterogeneous catalysts for Sonogashira coupling reactions, a PEG-OMe (Methoxy Polyene Glycol) - mediated method was developed to immobilize Pd/Cu bimetallic nanoparticles on activated carbon (AC). Catalytic experiments showed that Pd/Cu@AC prepared in a PEG-OMe 500 had the highest activity. The morphology and composition of the catalyst were determined, and the identified crystallized and heterometallic nanoparticles of Pd/Cu were essential for an efficient catalytic cycle. The Pd/Cu@AC catalyst was successfully used in Sonogashira reactions (21 examples) including with aryl bromides as the coupling partner in EtOH at 80–100 °C. The catalyst was recycled at least nine times. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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12 pages, 1206 KiB

Open AccessArticle

PdI₂ as a Simple and Efficient Catalyst for the Hydroamination of Arylacetylenes with Anilines

by Alessandra Casnati, Aleksandr Voronov, Damiano Giuseppe Ferrari, Raffaella Mancuso, Bartolo Gabriele, Elena Motti and Nicola Della Ca’

Catalysts 2020, 10(2), 176; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10020176 - 02 Feb 2020

Cited by 5 | Viewed by 3093

Abstract

The hydroamination reaction is a convenient alternative strategy for the formation of C–N bonds. Herein, we report a new versatile and convenient protocol for the hydroamination of arylacetylenes with anilines using palladium iodide in the absence of any added ligand as catalyst. Mild conditions, excellent regio- and stereoselectivity, and high functional group tolerance are the main features of this methodology. A subsequent reduction step gives access to a wide variety of secondary aromatic amines. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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8 pages, 2523 KiB

Open AccessArticle

Pd–Ce/ZIF-8 Nanocomposite for Catalytic Extraction of Sinomenine from Sinomenium acutum

by Yinghuai Zhu and Zhiyu Bai

Catalysts 2020, 10(2), 174; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10020174 - 02 Feb 2020

Cited by 6 | Viewed by 2639

Abstract

Sinomenine is a naturally occurring alkaloid and commonly used as one of the bioactive drug components in rheumatoid arthritis (RA) treatment in the clinic. Varying supported palladium-based catalysts have been synthesized and examined as heterogeneous catalysts for catalytic extraction of sinomenine from Sinomenium acutum. Among various examined supported catalysts, Pd–Ce/ZIF-8 (zeolitic imidazolate framework-8) demonstrates promising catalytic activity in the extraction reaction with an improved yield of 2.15% under optimized conditions. The catalyst composite can be recovered by centrifuging, and reused. A total of three catalyst recycling processes were performed with constant activity. The catalyst Pd–Ce/ZIF-8 has a particle size range of 2–12 nm and a total Pd–Ce loading amount of 5.1 wt% (ZIF-8). Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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15 pages, 2967 KiB

Open AccessArticle

A Polypyrrole-Modified Pd-Ag Bimetallic Electrode for the Electrocatalytic Reduction of 4-Chlorophenol

by Xuefeng Wei, Laiyuan Zeng, Weiwei Lu, Juan Miao, Ruichang Zhang, Ming Zhou and Jun Zhang

Catalysts 2019, 9(11), 931; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9110931 - 07 Nov 2019

Cited by 7 | Viewed by 2657

Abstract

A polypyrrole-modified bimetallic electrode composed of Pd-Ag on a Ti substrate (Pd-Ag/PPY/Ti) was successfully prepared via a chemical deposition method, and was applied to the electrocatalytic hydrodechlorination of 4-chlorophenol (4-CP) in aqueous solution. The electrode was characterized by cyclic voltammetry (CV), scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Various influences on the dechlorination efficiency of 4-chlorophenol, including applied current, initial pH value, and temperature, were studied. The dechlorination efficiency of 4-CP reached 94% within 120 min under the optimum conditions, i.e., a dechlorination current of 6 mA, an initial pH of 2.30, and a temperature of 303 K. The apparent activation energy of the dechlorination of 4-CP by the Pd-Ag/PPY/Ti electrode was calculated to be 49.6 kJ/mol. The equivalent conversion rate constant k_Pd was 0.63 L.g_Pd⁻¹·min⁻¹, which was higher than the findings presented in comparable literature. Thus, a highly effective bimetallic electrode with promising application prospects and low Pd loading was fabricated. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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14 pages, 4250 KiB

Open AccessArticle

Y-Modified MCM-22 Supported PdO_x Nanocrystal Catalysts for Catalytic Oxidation of Toluene

by Zhu Chen, Danna Situ, Jie Zheng, Zhen Cheng, Zhuo Wang and Shufeng Zuo

Catalysts 2019, 9(11), 902; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9110902 - 28 Oct 2019

Cited by 13 | Viewed by 3184

Abstract

A series of rare earth elements (REEs)-modified and Mobil Composition of Matter (MCM)-22-supported Pd nanocrystal catalysts were synthesized via a high-temperature solution-phase reduction method and tested for toluene complete oxidation. These catalytic materials were systematically characterized by N₂ adsorption/desorption, X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive spectroscopy (EDS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), temperature-programmed surface reaction of toluene (toluene-TPSR) and X-ray photoelectron spectroscopic (XPS) techniques in order to investigate the structure–catalytic property relationship. Moreover, catalysts with an appropriate yttrium content greatly improved the catalytic activity of 0.2%Pd/MCM-22. PdO_x (x = 0, 1) nanoparticles, ranging from 3.6 to 6.8 nm, which were well distributed on the surface of MCM-22. Efficient electron transfer from the Pd²⁺/Pd⁰ redox cycle facilitated the catalytic oxidation process, and the formation of Pd (or Y) –O–Si bonds improved the high dispersion of the PdO_x and Y₂O₃ particles. Toluene–TPSR experiments suggested that the addition of Y₂O₃ improved the physical/chemical adsorption of 0.2%Pd/MCM-22, thus increasing the toluene adsorption capacity. Then, 0.2%Pd/7.5%Y/MCM-22 exhibited the highest catalytic performance. In addition, this catalyst maintained 95% conversion with high resistance to water and chlorine poisoning, even after toluene oxidation at 210 °C for 100 h, making it more valuable in practical applications. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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16 pages, 2164 KiB

Open AccessArticle

Synthesis of Mono- and Bis-Pyrazoles Bearing Flexible p-Tolyl Ether and Rigid Xanthene Backbones, and Their Potential as Ligands in the Pd-Catalysed Suzuki–Miyaura Cross-Coupling Reaction

by Zahid Hussain, Cristiane Schwalm, Raoní Rambo, Renieidy Dias, Rafael Stieler and Adriano Monteiro

Catalysts 2019, 9(9), 718; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9090718 - 26 Aug 2019

Cited by 3 | Viewed by 3334

Abstract

The present work describes the synthesis of mono- and bis-pyrazole compounds bearing flexible p-tolyl ether and rigid 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene backbones as pyrazolyl analogues of DPEphos and Xantphos ligands, respectively. The synthesis of new pyrazolyl analogues was accomplished following an Ullmann coupling protocol, and the resulting products were isolated in overall good yields. In addition, a hybrid imidazolyl–pyrazolyl analogue bearing a xanthene backbone was synthesized using the same protocol, whereas a hybrid selanyl–pyrazolyl analogue with a xanthene backbone was synthesized in a good yield employing a second C–H activation step. The symmetrical bis-pyrazolyl and the hybrid imidazolyl–pyrazolyl analogues were found to be the most active among the new ligands evaluated in the Pd-catalysed Suzuki-Miyaura cross-coupling of aryl halides with aryl boronic acids. A simple catalytic system based on Pd(OAc)₂/2a was developed, which efficiently catalyses the Suzuki–Miyaura reaction of aryl halides and aryl boronic acids and provides moderate to excellent yields of the corresponding cross-coupling products. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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Review

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36 pages, 16307 KiB

Open AccessReview

A Review of Microwave-Assisted Synthesis-Based Approaches to Reduce Pd-Content in Catalysts

by Pranaw Kunal and Todd J. Toops

Catalysts 2020, 10(9), 991; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10090991 - 01 Sep 2020

Cited by 4 | Viewed by 3584

Abstract

This review article focuses on the latest advances in the synthesis of inorganic nano-catalysts using microwave heating, which has progressed significantly since its initial implementation in the mid-1980s. Over the years, nanoparticles (NPs), which inherently offer better surface accessibility for heterogeneous catalysis, have been synthesized using a wide array of heating methods. Microwave heating is one such method and employs a unique heating mechanism that can have several benefits for catalysis. When compared to conventional form of heating which relies on inter-layer mixing via convection, microwave heating operates through the chemical polarity in the target chemicals leading to an “inside-out” mode of heating. This heating mechanism is more targeted and therefore results in rapid synthesis of catalytically active NPs. Platinum group metals (PGM) have classically been the focus of nano-catalysis; however, recent efforts have also applied non-PGM group metals with the goals of lower costs, and ideally, improved catalytic reactivity and durability. This is especially of interest with respect to Pd because of its current historically high cost. Investigations into these new materials have primarily focused on new/improved synthetic methods and catalytic compositions, but it is important to note that these approaches must also be economic and scalable to attain practical relevance. With this overarching goal in mind, this review summarizes notable recent findings with a focus on Pd-dilution and microwave heating in a chronological fashion. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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38 pages, 9228 KiB

Open AccessFeature PaperReview

Palladium-Catalyzed Benzodiazepines Synthesis

by Michael S. Christodoulou, Egle M. Beccalli and Sabrina Giofrè

Catalysts 2020, 10(6), 634; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10060634 - 06 Jun 2020

Cited by 14 | Viewed by 5584

Abstract

This review is focused on palladium-catalyzed reactions as efficient strategies aimed at the synthesis of different classes of benzodiazepines. Several reaction typologies are reported including hydroamination, amination, C–H arylation, N-arylation, and the Buchwald–Hartwig reaction, depending on the different substrates identified as halogenated starting materials (activated substrates) or unactivated unsaturated systems, which then exploit Pd(0)- or Pd(II)-catalytic species. In particular, the use of the domino reactions, as intra- or intermolecular processes, are reported as an efficient and eco-compatible tool to obtain differently functionalized benzodiazepines. Different domino reaction typologies are the carboamination, aminoarylation, aminoacethoxylation, aminohalogenation, and aminoazidation. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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25 pages, 4199 KiB

Open AccessReview

Recent Developments in the Immobilization of Palladium Complexes on Renewable Polysaccharides for Suzuki–Miyaura Cross-Coupling of Halobenzenes and Phenylboronic Acids

by Adi Wolfson and Oshrat Levy-Ontman

Catalysts 2020, 10(1), 136; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10010136 - 18 Jan 2020

Cited by 18 | Viewed by 6018

Abstract

Polysaccharides derived from natural sources exhibit unique structures and functional groups, which have recently garnered them increased attention for their potential applicability as supports for metal catalysts. Renewable polysaccharide matrices were employed as supports for palladium complexes, with or without previous modification of the support, and were used in Suzuki cross-coupling of halobenzenes and phenylboronic acid derivatives. In this review, recent developments in the immobilization of palladium-based complexes are reported, including descriptions of the preparation procedures and catalytic activity of each system. In addition, the effects of the nature of the polymeric support and of the reaction conditions on catalytic performance are discussed. Full article

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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23 pages, 8455 KiB

Open AccessFeature PaperReview

The Reims Journey Towards Discovery and Understanding of Pd-Catalyzed Oxidations

by Jean Le Bras and Jacques Muzart

Catalysts 2020, 10(1), 111; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10010111 - 12 Jan 2020

Cited by 7 | Viewed by 4068

Abstract

This review recounts the development by the authors of the Pd-catalyzed procedures devoted to various kinds of oxidation. Starting with reactions assisted with UV light, the research has explored reactions under light-free conditions: allylic oxidation, alcohol oxidation, etherification, Wacker oxidation and dehydrogenations with, [...] Read more.

(This article belongs to the Special Issue Palladium-Catalyzed Reactions)

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