Article
Chemistry, Physical
Pavol Lopatka, Michal Gavenda, Martin Markovic, Peter Koos, Tibor Gracza
Summary: This work describes the total synthesis of jaspine B using highly diastereoselective Pd(II)-catalysed carbonylative cyclisation for the preparation of crucial intermediates. New conditions involving the use of pBQ/LiCl and Fe(CO)(5) were developed, and the application of a flow reactor in large-scale preparation of key lactones was demonstrated.
Article
Chemistry, Multidisciplinary
Xiaolei Ji, Chaoren Shen, Xinxin Tian, Hongru Zhang, Xinyi Ren, Kaiwu Dong
Summary: In this study, a Pd-catalyzed asymmetric double hydroxycarbonylation of terminal alkynes was developed using relay catalysis, which provided an efficient route to chiral succinic acids. This method demonstrated high yields and enantioselectivity for 41 examples and showcased its synthetic utilities in the facile synthesis of key intermediates for chiral pharmaceuticals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Ida Ziccarelli, Raffaella Mancuso, Francesco Giacalone, Carla Calabrese, Valeria La Parola, Alex De Salvo, Nicola Della Ca', Michelangelo Gruttadauria, Bartolo Gabriele
Summary: This article reports the successful heterogenization of the classical PdI(4)(2-)carbonylation catalyst on multi-walled carbon nanotubes. The newly developed heterogeneous catalyst shows good activity and recyclability in the oxidative monoaminocarbonylation reaction, with limited metal contamination in the final organic compounds.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Juan C. Caravez, Madison J. Wong, Rahul D. Kavthe, Balaram S. Takale, Bruce H. Lipshutz
Summary: Amides, acids, and thioesters can be easily formed from precursor aryl/heteroaryl halides under micellar catalysis conditions using W(CO)(6) as a carbon monoxide source. Palladium catalysts with ligands are usually loaded at around 0.5 mol%. Higher yields were obtained with iodides compared to bromides. Applications in the pharmaceutical industry and examples from the Merck Informer Library are demonstrated. E Factor calculations and options for recycling the aqueous reaction medium are also presented.
Article
Chemistry, Multidisciplinary
Csaba Arvai, Laszlo T. Mika
Summary: This review summarizes the recent applications of alternative solvents in improving the efficiency, safety, and environmental friendliness of carbonylation reactions. The use of water, biomass-based alcohols, ionic liquids, and other alternative solvents can enhance the reaction protocols.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Applied
Ding Ma, Chenyang Wang, Deshen Kong, Yongliang Tu, Peng Shi, Carsten Bolm
Summary: Palladium-catalyzed carbonylation reactions with Cr(CO)(6) as carbonyl source are key for the preparation of N-ynonylsulfoximines from NH-sulfoximines and bromoalkynes, affording the corresponding products in good yields at room temperature with a wide range of substrate combinations.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Xinyi Ren, Lin Tang, Chaoren Shen, Huimin Li, Peng Wang, Kaiwu Dong
Summary: A palladium-catalyzed asymmetric hydroesterification-cyclization method was developed for efficient preparation of enantioenriched gamma-lactams, with good selectivities and a broad substrate scope. The correlation between multiple selectivities and N-substitutes of the amide linker in the substrate was demonstrated through crystallographic evidence and control experiments.
Article
Chemistry, Physical
Pierre-Louis Lagueux-Tremblay, Celestin Augereau, Pranav Nair, Kwan Ming Tam, Bruce A. Arndtsen
Summary: The use of metal catalysis to form potent acylating agents is an important approach to expand the application of carbonylation reactions. However, the reductive elimination of these reactive products has been a challenge, making these reactions often high temperature, high pressure, and limited in scope. In this study, a mild and versatile palladium catalyzed carbonylative method was developed to generate electrophilic acyl-DMAP salts by exploiting the counterion. The weakly coordinating triflate anion was found to destabilize Pd(II) and enable irreversible reductive elimination, while ligand design facilitated the rapid activation of aryl or vinyl triflates. This approach allows palladium catalyzed carbonylations to be carried out under exceptionally mild conditions, with low catalyst loading and using readily available C(sp2)-triflate reagents.
Article
Chemistry, Physical
Pierre-Louis Lagueux-Tremblay, Celestin Augereau, Pranav Nair, Kwan Ming Tam, Bruce A. Arndtsen
Summary: The use of metal catalysis to form potent acylating agents is an important method to broaden the applicability of carbonylation reactions. However, the reductive elimination of these reactive products has presented a challenge, making the reactions often high temperature and high pressure, and limited in scope. In this study, a mild and versatile palladium catalyzed carbonylative method was developed to generate electrophilic acyl-DMAP salts. The use of triflate anion as a counterion destabilizes Pd(II) and allows for irreversible reductive elimination, while ligand design enables the rapid activation of aryl or vinyl triflates.
Article
Chemistry, Physical
Juan Camilo Arango-Daza, Carles Lluna-Galan, Luis Izquierdo-Aranda, Jose R. Cabrero-Antonino, Rosa Adam
Summary: A heterogeneous catalytic system for the acceptorless dehydrogenative condensation between N,N'-disubstituted ureas and 1,2-diols to produce imidazolones was developed. The designed palladium nanoaggregates on an alumina matrix showed good activity and selectivity, with wide applicability and moderate to good yields. Mechanistic studies and characterization were performed, revealing the key factors for the catalyst's activity. Furthermore, a Pd-Zn cooperation effect was described, and bimetallic materials were also designed and characterized properly.
Article
Chemistry, Organic
Fanni Bede, Laszlo Kollar, Nandor Lambert, Peter Huszthy, Peter Pongracz
Summary: Palladium-catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were successfully performed under carbon monoxide atmosphere. The targeted amides were synthesized in moderate to good isolated yields without the need for acidic additives. The effect of chiral diphosphines on product distribution, including chemo-, regio-, and enantioselectivities, was also investigated.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Yiwen Zhu, Zhengjie Le, Jun Ying, Xiao-Feng Wu
Summary: A palladium-catalyzed double carbonylation reaction has been developed for the rapid construction of 4-oxo-4-(aryl/alkylamino)butanoic acid scaffolds, using benzene-1,3,5-triyl triformate (TFBen) as the CO surrogate. The reaction with aromatic and aliphatic primary amines proceeded well, yielding a variety of functionalized acids in high yields.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chieh-Hung Tien, Alina Trofimova, Aleksandra Holownia, Branden S. Kwak, Reed T. Larson, Andrei K. Yudin
Summary: Carboxy-MIDA-boronate serves as both a precursor for heterocycle synthesis and an excellent in situ CO surrogate, demonstrating wide functional-group compatibility and high efficiency in various palladium-catalyzed transformations. An array of compounds can be synthesized in good-to-excellent yields using this strategy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Beata Gatlik, Wojciech Chaladaj
Summary: A Pd-catalyzed three-component protocol was developed for the direct synthesis of perfluoroalkyl-substituted alpha,beta-unsaturated esters using formates as convenient CO sources. The reaction proceeded smoothly under mild conditions with high yields and excellent selectivities. Detailed mechanistic studies supported by DFT calculations were conducted to understand the reaction pathway.
Article
Chemistry, Multidisciplinary
Taichi Kusakabe, Dongwei Liu, Kaori Tsuchida, Shun Okazaki, Tsuyoshi Hashimoto, Akane Mori, Kentaro Yoshiwaka, Hiroaki Sasai, Keisuke Takahashi, Keisuke Kato
Summary: The palladium-catalyzed methoxy-methoxycarbonylation of monosubstituted allenes was reexamined. It was found that arylallenes provided methyl 2-methoxymethylacrylates in good yield with moderate to good enantioselectivity, while alkylallenes afforded methyl 2-methoxymethylacrylates regioselectively but with low enantioselectivity.
Article
Chemistry, Applied
Aleksandr Voronov, Alessandra Casnati, Paolo P. Mazzeo, Paolo Pelagatti, Alessia Bacchi, Raffaella Mancuso, Bartolo Gabriele, Elena Motti, Giovanni Maestri, Peter Pal Feher, Andras Stirling, Nicola Della Ca'
Summary: A new method for the transformation of propargyl ureas to 2-aminooxazolines using Ag(I) catalysis is disclosed in this article, providing good yields and complete stereoselectivity. A one-pot protocol starting from propargylic amines and isocyanates has also been developed. Insights into the tautomeric equilibrium and relative reactivity of 2-aminooxazoles are provided.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Environmental Sciences
Vu T. Luong, Edgardo E. Canas Kurz, Ulrich Hellriegel, Duc N. Dinh, Hang T. Tran, Alberto Figoli, Bartolo Gabriele, Tran L. Luu, Jan Hoinkis
Summary: This study developed and tested a modular desalination system combining membrane capacitive deionization (MCDI) with low-pressure reverse osmosis (LPRO). The system was evaluated and compared with conventional seawater reverse osmosis (SWRO) at different salinities. The pilot tests conducted in the Can Gio region of South Vietnam showed that the system achieved drinking water quality with low energy consumption. The study also investigated fouling mitigation methods for the ultrafiltration pre-treatment.
JOURNAL OF ENVIRONMENTAL MANAGEMENT
(2023)
Article
Chemistry, Physical
Francesco Nocito, Marco Bortoluzzi, Michele Aresta, Angela Dibenedetto
Summary: This article presents interesting reactions between urea and biosourced diols, driven by cheap catalysts, which result in the elimination of ammonia and water. Various compounds, including cyclic carbonates, linear mono- and diurethanes, cyclic urethanes, and oligomeric urethanes, can be synthesized under mild conditions. ZnO and CeO2, as catalysts, exhibit different behavior in promoting ammonia or water elimination, with CeO2 being recoverable and reusable. CeO2 also facilitates the formation of oligo-urethanes through sequential diol-urea coupling.
Review
Chemistry, Physical
Bartolo Gabriele, Raffaella Mancuso, Nicola Della Ca, Lucia Veltri, Ida Ziccarelli
Summary: This article provides an overview of catalytic carbonylative double cyclization reactions, where organic substrates and carbon monoxide are sequentially activated to form two new cycles with the incorporation of carbon monoxide. It highlights the power of this synthetic methodology in the one-step synthesis of complex molecular architectures using readily available CO as the building block. The review is divided into five sections: Introduction, Functionalized Olefinic Substrates, Functionalized Acetylenic Substrates, Functionalized Halides, and Conclusions and Future Perspectives.
Review
Chemistry, Multidisciplinary
Bartolo Gabriele, Nicola Della Ca', Raffaella Mancuso, Lucia Veltri, Ida Ziccarelli
Summary: This microreview provides an overview of the recent advances (2020 to September, 2022) in synthetic methods using amidine and guanidine for carbon dioxide capture and utilization. The use of these superbases has shown to facilitate CO2 capture and the formation of stable carbamate salts. Furthermore, these superbases have also enabled the incorporation of CO2 into functionalized organic substrates.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Raffaella Mancuso, Alex De Salvo, Patrizio Russo, Aurelia Falcicchio, Nicola Della Ca, Leonardo Pantoja Munoz, Bartolo Gabriele
Summary: The PdI2/KI-catalyzed oxidative carbonylation of 4-(2-aminophenyl)-3-yn-1-ols selectively produces dihydrofuroquinolinone derivatives in fair to high yields (60%-89%) and excellent turnover numbers (180-267 mol of product per mol of Pd) over 19 examples. This reaction involves the catalytic construction of two rings and three new bonds in one step, providing high value added fused heterocyclic structures from readily available materials.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Editorial Material
Chemistry, Inorganic & Nuclear
Angela Dibenedetto, Alceo Macchioni
Summary: The CIRCC is an international consortium consisting of 17 universities and 75 research units in Italy. It focuses on developing new chemical reactions, catalytic systems, and their potential industrial applications. This article introduces the consortium to EurJIC readers and summarizes the scientific articles featured in the Institute Feature dedicated to CIRCC.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Mario Prejano, Raffaella Mancuso, Tiziana Marino, Bartolo Gabriele
Summary: In this study, a detailed computational investigation was conducted on the conversion of 1-(methylthio)-3-yn-2-ols to thiophene-3-carboxylate esters using PdI2/KI catalyst. The study provides insights into the role of each species involved in the reaction mechanism and confirms the experimental data.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Chiara Biribicchi, Andrea Macchia, Gabriele Favero, Romina Strangis, Bartolo Gabriele, Raffaella Mancuso, Mauro Francesco La Russa
Summary: This study investigates the use of hydrophobic Deep Eutectic Solvents (DESs) as alternatives to toxic solvents for removing nonpolar coatings from works of art. Beeswax and two microcrystalline waxes were tested, and the interaction between DESs and the waxes was evaluated using various tests. The results show that DESs have the potential to be used as green solvents for cleaning Cultural Heritage.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Ida Ziccarelli, Lucia Veltri, Tommaso Prestia, Roberta Amuso, Maria A. Chiacchio, Raffaella Mancuso, Bartolo Gabriele
Summary: Unreported 2-(4-acylfuran-2-yl)acetamides were selectively synthesized in fair to good yields (54-81%) over 19 examples through a mild catalytic process involving Csp-H activation, 5-exo-dig O-cyclization, and aromative isomerization.
