Review
Chemistry, Physical
Yong You, Qun Li, Yan-Ping Zhang, Jian-Qiang Zhao, Zhen-Hua Wang, Wei-Cheng Yuan
Summary: Palladium-catalyzed decarboxylative cycloadditions have emerged as highly efficient methods for constructing structurally diverse carbo- and heterocycles due to their ability to form multiple carbon-carbon or carbon-heteroatom bonds in a single step. This review discusses the achievements and synthetic applications of these reactions involving cyclic carbonates, carbamates, and lactones for accessing oxacyclo-, azacyclo-, and carbocyclic compounds. Mechanistic insights and the challenges and opportunities in this field are also addressed.
Article
Chemistry, Multidisciplinary
Oscar M. F. Lama, Diego A. Roa, Alma Arevalo, Juventino J. Garcia
Summary: The hydrodeoxygenation (HDO) of different fatty acids (FAs) was successfully achieved using commercially available nickel(II) compounds as catalysts and silanes as reducing agents under mild reaction conditions. By fine-tuning the reaction conditions and using relatively mild conditions without additives, high conversions (83% to >=99%) and good selectivity were obtained for the carboxylic group reduction of fatty acids, yielding aldehydes, alcohols, and hydrocarbons. The reaction mechanism was investigated using a synthesized and characterized reaction intermediate [Ni(C15H31COO)(2)(H2O)(2)], which demonstrated as an active catalyst.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Florian F. Mulks, Mohand Melaimi, Xiaoyu Yan, Mu-Hyun Baik, Guy Bertrand
Summary: Using computational methods, the redox potentials of BI-s derived from different types of stable carbenes were assessed, and the key parameters influencing the catalytic cycle were studied. It was found that most carbenes have higher reducing powers than thiazol-2-ylidene 1 and the 1,2,4-triazolylidene 2. The solvent polarity influences the reducing power of BI-s, but the redox potential of the oxidant increases at a greater rate, facilitating the reaction. The cation associated with the base also plays a role, especially in nonpolar solvents, with large and weakly coordinating cations being beneficial. Based on the results, mesoionic carbene 3 and abnormal NHC 4 are suggested as promising candidates for oxidative carbene organocatalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Qinglong Zhang, Weiwei Zi
Summary: The study presents a dual-metal catalyzed diastereodivergent coupling method for the synthesis of beta-amino alcohols with multiple stereoisomers, enabling the concise preparation of natural products such as mycestericins F and G.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Zipeng Wang, Tongxiang Cao, Shifa Zhu
Summary: The coupling reaction of enynal and enynol catalyzed by gold has been achieved by selectively steering two transient vinyl-gold intermediates, showing high atom economy and good tolerance of functional groups, with the reactivity being determined by the in situ formed vinyl-gold.
Article
Engineering, Chemical
Pablo Domenech, Betsy Kurisingal Joseph, Alex Toftgaard Nielsen, Anders Riisager
Summary: The alkylation of acetone with butanol was optimized to achieve high acetone conversion and high C11 selectivity with low catalyst loading.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Organic
Bruna Papa Spadafora, Francisco Wanderson Moreira Ribeiro, Jullyane Emi Matsushima, Elaine Miho Ariga, Isaac Omari, Priscila Machado Arruda Soares, Diogo de Oliveira-Silva, Elisangela Vinhato, J. Scott McIndoe, Thiago Carita Correra, Alessandro Rodrigues
Summary: This study reports the regio- and diastereoselective synthesis of oxazolidinones via a Pd-catalyzed vicinal C-N/C-Cl bond-forming reaction from internal alkenes of allylic carbamates. The products are obtained in high yields and excellent diastereoselectivities. Detailed mechanistic studies were carried out to describe the reaction process, including the role of Cu(ii) in a C-Cl bond-forming mechanism step.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Yong-Zhou Pan, Qiang Xia, Jin-Xiu Zhu, Ying-Chun Wang, Ying Liang, Hengshan Wang, Hai-Tao Tang, Ying-Ming Pan
Summary: This article presents a method for synthesizing 2-oxazolidinones using CO2 and allylic amines, while preserving the unsaturated double bonds. The method also shows applicability in the synthesis of six-membered heterocycles and allows for subsequent structural modification.
Review
Chemistry, Multidisciplinary
Yong You, Yan-Ping Zhang, Zhen-Hua Wang, Jian-Qiang Zhao, Jun-Qing Yin, Wei-Cheng Yuan
Summary: Copper-catalyzed decarboxylative reactions of propargylic cyclic carbonates/carbamates are an efficient way to construct various useful skeletons. The field has gained attention and made significant progress due to the reaction sites of propargylic cyclic carbonates/carbamates and the advantages of copper catalysis. This review addresses the achievements, mechanisms, synthetic applications, limitations, challenges, and opportunities in this field.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Lei Zhang, Chengyu Liu, Maolin Sun, Chaoming Liang, Liming Cao, Xiantong Yao, Yueyue Ma, Ruihua Cheng, Jinxing Ye
Summary: An iridium catalytic system using a ferrocene-based phosphine ligand with a modular and tunable unsymmetrical vicinal diamine scaffold was developed for the asymmetric hydrogenation of aryl ketones. This method provided a powerful tool for the enantioselective synthesis of diverse chiral alcohols, exhibiting excellent reactivity and enantioselectivity (yield up to 99%, ee up to 99%, and turnover number up to 50,000). The substituents and chirality of unsymmetrical diamines in the ligands played a crucial role in achieving satisfactory results.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Belen Lopez-Sanchez, Ana Belen Bohome-Espinosa, Franco Scalambra, Antonio Romerosa
Summary: The complex [RuCp(H2O-kappa O)(mPTA)(2)](CF3SO3)(3)center dot MeOH (4 center dot MeOH) was synthesized and its crystal structure determined by X-ray diffraction. The catalytic activity of 4 for the redox isomerization of 2-cyclohexen-1-ol into cyclohexanone was studied in different systems, with the highest conversion rate achieved in biphasic water/cyclohexane. The aqueous phase containing 4 was recycled up to 7 consecutive runs without significant losses of catalyst.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Michael Kohr, Uli Kazmaier
Summary: Protected dipeptides can be converted into cyclic ketoaminals, which can undergo palladium-catalyzed regioselective C-H functionalization. The use of the MTA directing group was found to be superior to the commonly used AQ group. Incorporation of modified dipeptides into larger peptide chains is possible after cleavage of the directing and protecting groups.
Article
Chemistry, Physical
Laila M. Nhari, Elham N. Bifari, Aisha R. Al-Marhabi, Huda A. Al-Ghamdi, Sameera N. Al-Ghamdi, Fatimah A. M. Al-Zahrani, Khalid O. Al-Footy, Reda M. El-Shishtawy
Summary: The fundamentals of Pd-catalyzed Csp(2)-Csp(2) Miyaura borylation, Suzuki cross-coupling, and Stille cross-coupling reactions for a variety of borylated precursors based on phenothiazine (PTZ), phenoxazine (POZ), carbazole (Cz), and quinoxaline (QX) units have been explored. Different palladium-based catalysts were employed under various reaction conditions to design and synthesize desired chromophores and pinacol boronate ester derivatives. Pd(dppf)Cl-2 was found to be the most effective catalyst for borylation, allowing for rapid C-C cross-coupling reactions with excellent yields. The Suzuki-Miyaura and Stille cross-coupling reactions showed efficient coupling between electron-rich and electron-deficient compounds, resulting in the synthesis of various chromophores.
Article
Chemistry, Physical
Giovanni Di Liberto, Gianfranco Pacchioni, Yang Shao-Horn, Livia Giordano
Summary: RuO2 and IrO2 are highly active catalysts for the Oxygen Evolution Reaction (OER), and the catalytic surface of these oxides plays a role in the reaction. Recent studies have shown that a hydrogen bond between the catalytic surface and a neighboring OH group stabilizes an unconventional -OO intermediate (-OO-H) before O-2 evolution. The presence of water molecules affects the stability and interconversion of -OOH and -OO-H oxygenates, highlighting the importance of including water in the model.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Jichao Xiao, Zhenning Li, John Montgomery
Summary: This study demonstrates a method using nickel catalysis and BiOx ligand for the reductive coupling of redox-active esters with aliphatic aldehydes to obtain silyl-protected secondary alcohols. The protocol is simple, mild, and tolerates a variety of functional groups, with potential mechanistic insights pointing towards a radical chain pathway.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Angela Dibenedetto, Francesco Nocito
Article
Chemistry, Physical
Davide M. S. Marcolongo, Francesco Nocito, Nicoletta Ditaranto, Michele Aresta, Angela Dibenedetto
Article
Engineering, Environmental
Eugenio Quaranta, Angela Dibenedetto, Francesco Nocito, Paola Fini
Summary: This study presents a novel approach to valorize potentially hazardous PC wastes by regenerating BPA monomers and repurposing waste PC into PUs through a non-isocyanate route. The PUs obtained showed thermally stability and high processing suitability, making them promising materials for various applications.
JOURNAL OF HAZARDOUS MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Francesco Nocito, Ilaria Orlando, Francesca Digioia, Michele Aresta, Angela Dibenedetto
Summary: This study describes the synthesis and application of mixed oxides as catalysts for the one-pot conversion of nonedible oils into C9 mono- and dicarboxylic acids, providing a cost-effective, recoverable, and reusable method for producing valuable products with potential applications in various industries. The research also highlights the use of oxygen as an oxidant, the elimination of sulfuric acid in esterification/transesterification, and the use of a single catalyst for both oxidation and esterification reactions, marking significant innovations in the field.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Physical
Davide Michele Stefano Marcolongo, Francesco Nocito, Nicoletta Ditaranto, Roberto Comparelli, Michele Aresta, Angela Dibenedetto
Summary: This study reports the synthesis and characterization of mixed metal oxides as p,n-junction photocatalysts, and demonstrates the correlation between the preparation technique and the properties of the materials. The optical and electronic properties of the materials were evaluated using spectroscopic and characterization techniques.
Article
Biochemistry & Molecular Biology
Michele Aresta
Summary: This paper discusses the changing reputation of carbon dioxide and its potential as an alternative raw material to fossil fuels. It compares fuels derived from atmospheric CO2 with biomass-derived fuels and concludes that they should receive the same subsidies.
Article
Chemistry, Multidisciplinary
Domenico Linsalata, Michele Aresta, Marco Bortoluzzi, Nicoletta Ditaranto, Francesco Nocito, Angela Dibenedetto
Summary: The reaction between ethene glycol (EG) and CO2 to form cyclic ethene carbonate (EC) was studied under solvent-less conditions. Optimal reaction conditions were determined and the use of pervaporation membranes was found to increase the EC concentration. A DFT study showed that etherification and carbonation were competing reactions.
JOURNAL OF CO2 UTILIZATION
(2022)
Review
Biochemistry & Molecular Biology
Carmela Di Spiridione, Michele Aresta, Angela Dibenedetto
Summary: This article reviews the research progress of utilizing enzymatic cascade reactions to reduce CO2 to methanol, focusing on enzyme immobilization and cofactor regeneration. The process is briefly explained, and advancements in research are discussed, particularly in comparing enzymatic regeneration with chemical, electrochemical, and photochemical conversion of NAD(+) to NADH. The article also explores alternative solutions, such as reducing the amount of NADH used or substituting it with less expensive mimetic molecules, in order to further facilitate the industrial application of the process.
Article
Chemistry, Multidisciplinary
Francesco Nocito, Nicoletta Ditaranto, Domenico Linsalata, Mario Naschetti, Roberto Comparelli, Michele Aresta, Angela Dibenedetto
Summary: In this paper, the use of MnO2@CeO2 core-shell oxide as a catalyst for the oxidation of furfural into furoic acid in water solvent was described. The catalyst exhibited excellent catalytic properties and its activity was compared with commercial MnO2. The effects of calcination temperature, furfural solution concentration, and reaction conditions on the furoic acid yield were evaluated. The presence of biocomponents in the furfural samples affected the oxidation rate, but not the selectivity of the catalyst.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Inorganic & Nuclear
Michele Aresta
Summary: This paper chronicles the recent history of CO2 chemistry through contributions from CIRCC members, focusing on the coordination mode and reactivity of CO2, as well as its applications and challenges in various fields. It emphasizes carbon recycling as a crucial aspect of future energy and chemical innovation.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
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.
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)