Article
Chemistry, Physical
Laura J. McKay, Carl-Johan Carling, Neil R. Branda
Summary: Two novel photoremovable protecting groups in the benzoin class with improved molar extinction coefficients and extended absorptions towards the visible region have been prepared, yet their characteristics may not always translate to photoresponsive efficacy.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2021)
Article
Chemistry, Organic
Cristian Cavedon, Eric T. Sletten, Amiera Madani, Olaf Niemeyer, Peter H. Seeberger, Bartholomaeus Pieber
Summary: A visible-light-mediated debenzylation method has been proposed to make benzyl ethers temporary protective groups, enabling new orthogonal protection strategies and compatibility with multiple functional groups simultaneously.
Article
Chemistry, Organic
Ayushee, Monika Patel, Priyanka Meena, Kousar Jahan, Prasad Bharatam, Akhilesh K. Verma
Summary: A base-promoted protocol was investigated for the intermolecular anti-Markovnikov hydroamidation of vinyl arenes, leading to the formation of arylethylbenzamides with excellent chemo- and regioselectivity. The reaction demonstrated high chemoselectivity for the amide group over amine and tolerance towards a wide variety of functional groups. The proposed mechanism and the importance of the solvent were supported by deuterium labeling studies and control experiments.
Article
Chemistry, Organic
Jules Brom, Antoine Maruani, Laurent Micouin, Erica Benedetti
Summary: We have developed a practical method for performing the reductive photocleavage of sulfonamides using thioureas as organophotocatalysts. This transformation can tolerate a variety of substrates and occurs under mild reaction conditions in the presence of tetrabutylammonium borohydride as a reducing agent. Experimental and theoretical mechanistic investigations have revealed the nature of the active species involved in the photocatalytic process.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Minghui Wei, Jingming Zhang, Chengkou Liu, Wei He, Tingyu Wang, Xiaobing Yang, Zhao Yang, Zheng Fang, Kai Guo
Summary: A green and efficient reaction route for the synthesis of pyrrolidin-2-ones has been developed via photoinduced organocatalyzed three-component cyclization in a microchannel reactor under visible light conditions. The process can be carried out under mild conditions without using a metal, and a reasonable reaction mechanism was proposed based on control experiments.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Medicinal
Annie R. Hooper, Alexander S. Burns
Summary: In this study, a masking strategy using acrylamides is reported, allowing the introduction of masked functionality early in a synthetic route and specific thermal deprotection. The stability of acrylamide adducts is influenced by solvent and structural factors, as determined through kinetic studies. This protection strategy improves the yield of base-promoted reactions.
ACS MEDICINAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Organic
Kazuma Nishimura, Ryohei Hanzawa, Tomoya Sugai, Haruhiko Fuwa
Summary: The intramolecular double hydro-functionalization of internal alkynes catalyzed by [RuCl2(p-cymene)](2)/AgNO3 resulted in the synthesis of a series of spirocyclic hemiaminal ether derivatives in good to excellent yields. The product spiro-hemiaminal ethers underwent Lewis acid-mediated chemoselective cleavage to generate in situ iminium/oxocarbenium ions that could be further reacted with nucleophiles to afford a range of nitrogen and oxygen heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Patrick S. Fier, Riley A. Roberts, Reed T. Larson
Summary: We have developed a method for converting esters to ketones in a single step using simple reagents. This selective transformation is achieved by activating the adjacent carbon to deprotonation through the use of a transient sulfinate group on the nucleophile, allowing the formation of a carbanion that adds to the ester. This reaction is then followed by another deprotonation step to prevent further addition, and the resulting dianion spontaneously fragments the SO2 group upon quenching with water to produce the ketone product.
Article
Chemistry, Multidisciplinary
Nikitas G. Malliaros, Michael Orfanopoulos
Summary: A direct and selective functionalization of C60 with amides and lactams has been successfully developed utilizing diverse radicals derived from carboxy, sulfonyl, phosphoramides, and lactams. This novel approach relies on a hydrogen atom transfer process mediated by tetrabutylammonium decatungstate [(n-Bu4N)4W10O32]. The addition of these carbon-centered radicals to [60] fullerene produces a new class of unexplored fullerene-based materials, with important structural insight provided by dynamic NMR spectroscopy and a proposed mechanism based on reaction product structures and kinetic studies.
JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS
(2023)
Article
Chemistry, Organic
Hiroaki Kurouchi
Summary: A new synthesis method has been developed for the direct amidation of aromatic-ring-tethered N-carbamoyl tetrahydroisoquinoline substrates, allowing for the general access to 8-oxoberberines and their homologues while overcoming undesired tandem side-reactions that result in the destruction of the isoquinoline backbone observed in previous methods.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Piotr Szczesniak, Bartlomiej Furman
Summary: The protocol developed in this study utilizes a photo-induced intramolecular Fries-type rearrangement to prepare structurally diverse enaminones efficiently. This method features mild reaction conditions, broad substrate applicability, high economic feasibility, and reduced waste production. The methodology was successfully applied as a key step in the synthesis of the important fragrance compound dihydrojasmone.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Manuel Freis, Moritz Balkenhohl, David M. Fischer, Tony Georgiev, Roman C. Sarott, Erick M. Carreira
Summary: The cobalt-catalyzed aminocyclization of unsaturated N-acyl sulfonamides in the presence of oxygen was reported, leading to the formation of α- and d-lactam aldehydes. Enantiomerically enriched α- and d-lactam alcohols were obtained by using an optically active cobalt catalyst. The obtained α-lactam aldehydes and alcohols were further elaborated into useful building blocks.
Article
Chemistry, Organic
Manuel Freis, Moritz Balkenhohl, David M. Fischer, Tony Georgiev, Roman C. Sarott, Erick M. Carreira
Summary: This paper reports a cobalt-catalyzed aminocyclization of unsaturated N-acyl sulfonamides in the presence of oxygen, leading to α- and d-lactam aldehydes. Chiral cobalt catalysts were utilized to obtain enantiomerically enriched α- and d-lactam alcohols. The α-lactam aldehydes and alcohols obtained can be elaborated into useful building blocks.
Article
Chemistry, Multidisciplinary
Yun-Chao Zhang, Yang Chen, Jing Sun, Jing-Yun Wang, Ming-Dong Zhou
Summary: A visible-light-induced tandem radical intramolecular cyclization/arylation of quinoxalin-2(1H)-ones with bromodifluoroacetamides is described, leading to the efficient synthesis of valuable α,α-difluoro-γ-lactam-fused quinoxalin-2(1H)-ones. This metal-free, mild, and redox neutral reaction protocol is tolerant of various functional groups and substrates, providing moderate to good yields.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Organic
Mehmet Murat Kisla, Mohammed Al-Kassim Hassan, Hind M. Osman, Amine Sena Aydin, Hasan Tahsin Sen, Shan Khazei, Pinar Kul, Canan Kus
Summary: The use of protecting groups in organic chemistry has been successful in synthesizing a variety of useful organic compounds and addressing complexities in organic reactions. These protecting groups find applications in simple and complex reactions involving the synthesis of large organic compounds such as peptides and oligosaccharides. Ideal protecting groups are utilized to prevent undesired reactions and achieve desired objectives.
CURRENT ORGANIC SYNTHESIS
(2023)
Article
Chemistry, Physical
Riccardo Capelli, Francesco Muniz-Miranda, Giovanni M. Pavan
Summary: Despite significant efforts, simulating water still poses challenges and questions. By utilizing a data-driven approach, this study reveals that classical models can capture the formation of transient ice-like environments in liquid water, consistent with recent ab initio calculations.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Polymer Science
Monika Flejszar, Kinga Slusarczyk, Pawel Chmielarz, Karol Wolski, Abdirisak A. Isse, Armando Gennaro, Magdalena Wytrwal-Sarna, Marcin Oszajca
Summary: This paper describes a new method, surface-initiated simplified electrochemically mediated ATRP (SI-seATRP), for the fabrication of patterned polymer brushes at the microliter scale. The research demonstrates that by selecting the appropriate surface and shape of the working electrode, polymerization reactions can be conducted directly on the laboratory bench with minimal reagents and a catalytic complex. This method allows for the formation of unique patterns in the polymers.
Article
Chemistry, Physical
Fabrizio Roncaglia, Adele Mucci, Marcello Romagnoli, Luca Spinelli, Alessandro di Bona, Roberto Biagi
Summary: To sustain the Hydrogen Economy, proton exchange membrane (PEM) devices are crucial for the generation and utilization of clean hydrogen. This study focuses on the technical improvement and cost reduction of bipolar plates, an essential part of PEM devices, by using cheap and commercially available graphite-epoxy composites. By adjusting the formulation and processing conditions, materials with desired electrical conductivity and gas permeability were successfully achieved. The processability and productivity of the method were improved, and the effect of molding pressure on the properties of the samples was analyzed.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Review
Biochemistry & Molecular Biology
Maurizio Muniz-Miranda, Francesco Muniz-Miranda, Maria Cristina Menziani, Alfonso Pedone
Summary: Density functional theory (DFT) calculations can reproduce the surface-enhanced Raman scattering (SERS) spectra and provide valuable information about the anchoring mechanism, bond strength, and structural modifications of molecules adsorbed on nanostructured metal surfaces. These findings are of fundamental importance for the application of SERS spectroscopy. This review discusses several SERS-DFT studies conducted in Italy and highlights the combination of experimental SERS spectra and DFT modeling to extract information. It also presents recent advancements and studies on the DFT approach to SERS spectroscopy along with commentary.
Article
Biology
Veronica D'Eusanio, Daniele Malferrari, Andrea Marchetti, Fabrizio Roncaglia, Lorenzo Tassi
Summary: Grape seeds are an important byproduct of wine production, from which edible oil is extracted. The residual defatted grape seeds can be used for composting or converted into biochar. This study analyzed the chemical composition of defatted grape seeds and found that they can be used as a dietary supplement or as an enriching ingredient in food for health benefits.
Article
Chemistry, Inorganic & Nuclear
Alessio Nicolini, Trey C. Pankratz, Marco Borsari, Rodolphe Clerac, Antonio Ranieri, Mathieu Rouzieres, John F. Berry, Andrea Cornia
Summary: Two tripodal oligo-& alpha;-pyridylamido ligands with interdigitated branches and 26 nitrogen donors form a trigonally symmetric coordination nanospace that accommodates a mixed valence iron cluster of much lower symmetry. This compound exhibits a large room-temperature magnetic moment and behaves as a single-molecule magnet, offering an appealing route to polyiron complexes. Bond valence sum (BVS) analysis and density functional theory (DFT) calculations were used to establish the protonation state of oxygen atoms and the formal oxidation states of the metals, revealing the structure and properties of the compound. Broken-symmetry DFT calculations predict strong ferromagnetic coupling between the two iron(II) ions, leading to a local S = 4 state that persists to room temperature and explaining the large magnetic moment measured at 300 K. The compound behaves as a single-molecule magnet, with detectable magnetization dynamics dominated by an Orbach-like mechanism.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Marianna Tosato, Sara Franchi, Abdirisak Ahmed Isse, Alessandro Del Vecchio, Giordano Zanoni, Andre Alker, Mattia Asti, Thomas Gyr, Valerio Di Marco, Helmut Maecke
Summary: To prevent the reduction of Cu2+ to Cu+ in vivo, researchers have developed a new type of complex that can better stabilize both oxidation states of copper ions by using a smaller macrocyclic backbone. This new complex also showed higher stability in human serum compared to previous complexes.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Lorenzo Franco, Abdirisak Ahmed Isse, Antonio Barbon, Lina Altomare, Viivi Hypponen, Jessica Rosa, Venla Olsson, Mikko Kettunen, Lucio Melone
Summary: This paper presents the synthesis, characterization, and in vivo application of water-soluble supramolecular contrast agents for MRI. The contrast agents were obtained from β-cyclodextrin functionalized with different nitroxide radicals. The experiments showed that the contrast agents had improved stability in vitro and in vivo, and were non-cytotoxic at low concentrations. The MRI experiments on glioma-bearing rats demonstrated a good lowering of T-1 relaxation in the tumor, indicating the potential of these contrast agents for improved tumor imaging.
Article
Chemistry, Analytical
Miriam Chavez, Jie Luo, Guadalupe Sanchez-Obrero, Marco Fantin, Rafael Madueno, Abdirisak Ahmed Isse, Jose Manuel Sevilla, Manuel Blazquez, Teresa Pineda
Summary: Electrochemically mediated surface-initiated atom transfer radical polymerization (SI-eATRP) is a technique used to grow controlled polymeric films from various surfaces. In this study, compact poly-(oligo(ethylene glycol)methacrylate) (p-OEGMA) brushes were tailored on gold electrodes using a combination of self-assembled monolayers (SAMs) and SI-eATRP. The effects of SAM-initiator nature, applied potential, and duration of polymerization were investigated, and the living character of the polymerization was demonstrated. The properties of the tailored p-OEGMA brushes were analyzed using cyclic voltammetry and electrochemical impedance spectroscopy, and their formation was confirmed by various characterization techniques.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Francesca Lorandi, Marco Fantin, Hossein Jafari, Adam Gorczynski, Grzegorz Szczepaniak, Sajjad Dadashi-Silab, Abdirisak A. Isse, Krzysztof Matyjaszewski
Summary: Linear free energy relationships (LFERs) were used to establish the reductive cleavage of the C(sp(3))-X bond in alkyl halides (RX) by Cu complexes. The activation rate constant, k(act), for 107 Cu complex/RX couples in 5 different solvents were effectively interpolated by an equation. The set of descriptors determined the fundamental properties of Cu complexes and RX, which need to be considered when designing atom transfer radical reactions. A multivariate linear regression (MLR) approach was adopted to develop an objective model that surpassed the predictive capability of the LFER equation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Physical
Marco Fantin, Abdirisak Ahmed Isse
Summary: This review explores the application of atom transfer radical polymerization (ATRP) in modifying electrode surfaces and creating functional materials for electrochemical purposes. It emphasizes the advantages of using ATRP-based polymers for the fabrication of supercapacitors, electrocatalysts, and ultra-sensitive electrochemical sensors.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Alessio Nicolini, Biagio Anderlini, Fabrizio Roncaglia, Andrea Cornia
Summary: A new polynucleating tripodal proligand H6tren(dpa)3 containing thirteen nitrogen donors of four different types was designed, synthesized, and isolated via a transition-metal-free triple N-arylation reaction. The use of Cs2CO3 as a base was essential for achieving high regioselectivity and eliminating overarylation almost completely. HFdpa was prepared with excellent yield by reaction of 2,6-difluoropyridine with 2-aminopyridine and found to be more reactive than HBrdpa, affording higher conversion and yield.
COMPTES RENDUS CHIMIE
(2023)
Article
Polymer Science
Gianluca Gazzola, Andrea Antonello, Abdirisak A. Isse, Marco Fantin
Summary: An electrochemically controlled atom transfer radical polymerization (eATRP) was successfully performed using a minimal amount of FeBr3 catalyst in a nonpolar solvent. The use of electrocatalytic methods in a highly nonpolar polymerization medium allowed for precise control over the polymerization process. Additionally, the setup of an undivided cell with simple iron wire electrodes significantly reduced electrical resistance and enabled the production of polymers with low dispersity. Examination of kinetic and thermodynamic aspects indicated that the high ATRP equilibrium constant of Fe catalysts in nonpolar environments facilitated ppm-level catalysis.
Article
Chemistry, Inorganic & Nuclear
Manuel Imperato, Alessio Nicolini, Marco Borsari, Matteo Briganti, Mario Chiesa, Yu-Kai Liao, Antonio Ranieri, Arsen Raza, Enrico Salvadori, Lorenzo Sorace, Andrea Cornia
Summary: We investigated the performance of heterobimetallic lantern complexes [PtVO(SOCR)4] as charge neutral electronic qubits based on vanadyl complexes. The results showed that these complexes exhibit good spin coherence properties, making them suitable for applications in materials science and quantum technologies.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Arsen Raza, Adele Mucci, Alessio Nicolini, Andrea Cornia
Summary: Lithium oligo-alpha-pyridylamides are useful intermediates in coordination chemistry, and can be used to synthesize extended metal atom chains with variable coordination numbers.
CHEMISTRY-SWITZERLAND
(2022)
