Article
Chemistry, Inorganic & Nuclear
Fei Fang, Jia-Xin Kang, Cong-Qiao Xu, Jiarui Chang, Jie Zhang, Shujun Li, Xuenian Chen
Summary: The influence of the pincer platform composition and substitution on the reactivity and physical properties of pincer complexes is easily explored experimentally, with subtle effects on the molecular structures and thermodynamic stability. The bond lengths and strengths of M-C-ipso, M-P, and M-X were discussed, along with thermochemical balances for different types of pincer complexes.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zachariah J. Berkson, Lukas Laetsch, Julius Hillenbrand, Alois Fuerstner, Christophe Coperet
Summary: This study demonstrates that Mo-95 chemical shift tensors in the context of alkyne metathesis provide detailed information on the electronic structure of catalysts and are directly linked to reactivity. The Mo-95 chemical shifts are driven by ligand electronegativity and electron delocalization, explaining the reactivity patterns of specific catalyst families. These results further motivate exploration of transition metal NMR signatures and their relationships to electronic structure and reactivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Samuel R. Zarcone, Peter J. Verardi, Nattamai Bhuvanesh, John A. Gladysz
Summary: This study reports a method for synthesizing novel cage-like complexes, which involves the reaction of a series of precursor compounds and coordination chemistry to obtain the target compounds. The structures and isomers of the target compounds were determined by crystallography.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yiran Wang, Matthew L. Nisbet, Kendall R. Kamp, Emily Hiralal, Romain Gautier, P. Shiv Halasyamani, Kenneth R. Poeppelmeier
Summary: The design of noncentrosymmetric (NCS) solid state materials, specifically how to break inversion symmetry between enantiomers, has been a subject of interest for chemists, physicists, and materials scientists. In this study, five new racemic compounds were synthesized and found to crystallize in centrosymmetric (CS) space groups, wherein the formation of an inversion center is attributed to parallel heterochiral π-π stacking interactions between adjacent Cu racemates. This work presents a conceptual framework and practical approach for understanding the absence of inversion symmetry in racemates in all NCS crystal classes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ryo Sumitani, Daisuke Kuwahara, Tomoyuki Mochida
Summary: Cationic rhodium complexes with 1,5-cyclooctadiene (cod) ligands were synthesized and their solid-state structures, thermal properties, and reactivities were investigated. The phase transitions of these salts resulted in disordered solid-state structures, with an increase in structural disorder as the cation symmetry decreased. FSA salts showed lower crystal symmetry and less cation disorder compared to SbF6 salts. Additionally, thermal stabilities and reactivities of these salts were studied, revealing different reactions upon melting for FSA and SbF6 salts.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Jakub Chalupsky, Martin Srnec
Summary: This study provides unprecedented insights into the exchange-coupling mechanisms between the magnetic centers in bis-mu-oxo bimetallic complexes, highlighting the essential and counterintuitive role of predominantly unoccupied valence metal d orbitals in strong antiferromagnetic coupling. This discovery sheds light on a new mechanism of exchange interaction between magnetic transition metal centers, enhancing our understanding of their catalytic and magnetic properties.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Inorganic & Nuclear
Ming-Yue Ju, Zi-Heng Fan, Yubin Ma, Yi Jing, Xi-Meng Chen, Xuenian Chen
Summary: Recent research has focused on the synthesis, structures, and reactivities of N-heterocyclic carbene-coordinated boranes. A synthetic method to access NHC center dot BH2NH2 was developed, and its reactivity with HCl or HOTf was investigated. The introduction of NHC molecules had a significant impact on the solubility and reactivities of aminoboranes.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Gracjan Kurpik, Anna Walczak, Mateusz Goldyn, Jack Harrowfield, Artur R. Stefankiewicz
Summary: A wide range of functionalized pyridine ligands have been used to synthesize various Pd(II) complexes with different structures. The functionalization of ligand molecules has a significant impact on the physicochemical properties of the coordination compounds. The study also reveals the relationship between NMR chemical shifts and ligand basicity. Furthermore, weak interactions have been identified through detailed crystallographic analysis, which explains the solution chemistry of the complexes. These Pd(II) complexes show efficient and versatile catalytic activity in Suzuki-Miyaura and Heck cross-coupling reactions.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Felix Depenbrock, Thomas Limpke, Eckhard Bill, Daniel J. SantaLucia, Maurice van Gastel, Stephan Walleck, Jan Oldengott, Anja Stammler, Hartmut Boegge, Thorsten Glaser
Summary: Peroxo complexes are crucial in water oxidation catalysis, and cobalt can exist as cobalt oxides or {Co-III(mu-1,2-peroxo)Co-III} complexes. This study presents the synthesis and characterization of {Co-III(mu-1,2-peroxo)(mu-OH)Co-III} and {Co-III(mu-OH)(2)Co-III} complexes, and reveals their catalytic activity in water oxidation.
INORGANIC CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Robert Czarnomysy, Dominika Radomska, Olga Klaudia Szewczyk, Piotr Roszczenko, Krzysztof Bielawski
Summary: New, safer, and more effective agents are needed for cancer treatment. Cytostatics with transition metals are attracting renewed interest from scientists, who are exploring combination therapy and molecular modifications to enhance effectiveness and selectivity. Recent drug findings with palladium and platinum atoms are being organized.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Inorganic & Nuclear
Bijoy Ghosh, Felipe Fantuzzi, Ashwini K. Phukan
Summary: Density functional theory calculations were conducted on metallatranes containing group 13 elements at the bridgehead position to study the M center dot center dot center dot Z interaction and reactivity at the metal center. The strength of the M center dot center dot center dot Z interaction was found to increase with the size and polarizability of the bridgehead group 13 elements. The binding of Lewis bases to the metallatranes was significantly more exergonic for the larger In(III) ions.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Maxym Tansky, Zipeng Gu, Robert J. Comito
Summary: This report introduces a new method for the synthesis of bis(pyrazolyl)alkanes, avoiding common issues in traditional methods and suitable for systematic ligand optimization. Additionally, new reactants including pyrazoles and aldehydes have been explored, providing a new direction for the development of novel catalysts.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Jun Du, Xiuyan He, Dongjing Hong, Shuangliu Zhou, Huayi Fang, Peng Cui
Summary: Heterobimetallic Ln(iii)-Pd(0) complexes with tetranuclear structures have been synthesized and their properties studied.
DALTON TRANSACTIONS
(2022)
Review
Endocrinology & Metabolism
Lijing Guo, Shihua Chen, Liping Ou, Shangmei Li, Zhen-Nan Ye, Hua-Feng Liu
Summary: Alpha-ketoglutarate (AKG) is a key intermediate in various metabolic pathways, participating in metabolism and signaling pathways. Kidney diseases are linked to metabolic disorders, and recent research focuses on the protective effects of AKG on healthy aging, which provides potential strategies for developing novel therapies.
DIABETES METABOLIC SYNDROME AND OBESITY-TARGETS AND THERAPY
(2022)
Article
Chemistry, Organic
Ryu Yamasaki, Mariko Ono, Kento Morita, Ai Ito, Kazuo Fukuda, Iwao Okamoto
Summary: Methyl substitution at the double bond of N-alkenyl anilides affects both the preferred conformation and susceptibility to acidic hydrolysis. Substitution at the R-1 position favors the trans conformation, while substitution at the R-2 or R-3 position favors the cis conformation. Substitution at the R-1 and R-3 positions increases the ratio of the trans conformer. DFT study reveals that these conformational preferences can be explained by torsion twisting induced by the substituent on the N-alkenyl moiety relative to the amide plane. R-1 substitution enhances susceptibility to acidic hydrolysis, while R-2 or R-3 substitution increases stability. The effect of the double bond on conformational preferences is demonstrated by comparing the preferred conformation of R-1-substituted anilide (trans) and hydrogenated N-isopropyl amide (cis).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Carlotta Raviola, Cristina Carrera, Massimo Serra, Alessandro Palmieri, Gabriele Lupidi, Giovanni Maestri, Stefano Protti
Summary: The photoreactivity of (E)-beta-nitroenones involves competitive pathways of stereoisomerisation to (E)-beta-nitroenones and deconjugation to beta-nitro-beta,gamma-enones, both originating from the triplet excited state of the starting substrates.
Article
Chemistry, Organic
Xiaoshuang Wang, Lei Sun, Miaomiao Wang, Giovanni Maestri, Max Malacria, Xiang Liu, Yanlan Wang, Lingang Wu
Summary: Aromatic triangular tri-palladium cations have shown excellent activities and selectivity in catalytic reactions. Efficient coupling reactions can be achieved with the appropriate palladium loading, resulting in high yields.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Frederic Celerse, Theo Jaffrelot Inizan, Louis Lagardere, Olivier Adjoua, Pierre Monmarche, Yinglong Miao, Etienne Derat, Jean-Philip Piquemal
Summary: The study presents a novel multilevel enhanced sampling strategy based on GaMD, implementing GaMD multi-GPU acceleration and dual-water mode in Tinker-HP to speed up solvent-solute interactions. By coupling GaMD with Umbrella Sampling, the convergence time of PMF is reduced significantly, and the introduction of Adaptive Sampling further enhances convergence speed, making it applicable for large-scale biological system simulations.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Multidisciplinary
Andrea Serafino, Maurizio Chiminelli, Davide Balestri, Luciano Marchio, Franca Bigi, Rai-mondo Maggi, Max Malacria, Giovanni Maestri
Summary: Visible-light-promoted dimerization of arylacryloyl allenamides can be achieved at room temperature using an iridium(III) photocatalyst. This reaction leads to the formation of complex molecular architectures with high selectivity, and the outcome is determined by the substitution pattern of the alkene.
Review
Chemistry, Physical
Gianpiero Cera, Giovanni Maestri
Summary: This review presents the method of converting alkynes into reactive allylmetal species by merging palladium and Bronsted acid catalysts, which has been used in developing new C-C and C-Het bond forming methodologies, and has wide applications in polymer chemistry, deuterium-labeling, and stereoselective catalysis.
Editorial Material
Chemistry, Physical
Etienne Derat, Shina Caroline Lynn Kamerlin
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
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
Chemistry, Multidisciplinary
Maurizio Chiminelli, Andrea Serafino, Davide Ruggeri, Luciano Marchio, Franca Bigi, Raimondo Maggi, Max Malacria, Giovanni Maestri
Summary: Dearomative cycloadditions offer a powerful method to access a vast chemical space using simple and ubiquitous building blocks. However, the loss of aromaticity has limited their synthetic potential. We have devised a general intramolecular method that overcomes this limitation by photosensitizing allenamides. This visible-light-promoted process produces complex [2.2.2]-(hetero)-bicyclooctadienes at room temperature, potentially stabilizing transient (bi)radicals through naphthalene. The reaction is tolerant of various functional groups, making it suitable for a wide range of applications, including the synthesis of isoindoles and metal complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Marc Petit, Cassandre C. Bories, Geoffrey Gontard, Marion Barbazanges, Etienne Derat
Summary: We achieved an efficient regio- and chemoselective dearomatization of N-heteroarenes using hydrido-cobalt catalysts. Mild conditions were employed and the reaction exclusively produced the silyl-1,2-dihydroheteroarenes in a wide range of N-heteroarenes. Quinolines and pyridines with electron-donating and electron-withdrawing substituents were compatible with this methodology. DFT calculations, NMR spectroscopic studies, and X-ray diffraction analysis demonstrated the importance of a second silane for the final step of the reaction.
Article
Chemistry, Multidisciplinary
Vinayak Botla, Marco Fontana, Aleksandr Voronov, Raimondo Maggi, Elena Motti, Giovanni Maestri, Nicola Della Ca'
Summary: Despite the advances in carbon-halogen bond formation, the selective functionalization of iodoaryls is still challenging. In this study, a one-pot synthesis of ortho-iodobiaryls from aryl iodides and bromides is reported using palladium/norbornene catalysis. The Catellani reaction involves the cleavage of a C(sp(2))-I bond, ortho C-H activation, oxidative addition of an aryl bromide, and restoration of the C(sp(2))-I bond, leading to the formation of palladacycles. A variety of valuable o-iodobiaryls have been synthesized with good yields, and their derivatization is described. A DFT study provides insights into the mechanism of the key reductive elimination step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Nicola Camedda, Franca Bigi, Raimondo Maggi, Giovanni Maestri
Summary: A sequential strategy enables the challenging assembly of dihydronaphthalenes through the key annulation of an alkyne with a vinylarene under mild conditions. The products are obtained in good yields and exhibit high functional tolerance, thanks to the domino nucleophilic substitution and dearomative Diels-Alder and ene reactions. DFT modeling data suggest that alkali cations play a crucial role in ensuring a smooth dearomative cyclization of the in situ generated intermediates.
Article
Chemistry, Organic
Andrea Serafino, Giovanni Maestri
Summary: The synthetic relevance of bicyclo[2.2.2]octadienes is demonstrated by their successful application in various chemical domains, and there is an ongoing interest in the concise assembly of these bridged bicycles. This article presents seminal strategies for crafting these compounds, as well as more recent applications utilizing visible light. A general intramolecular method for the para-cycloaddition of an allenamide arm onto simple aryl rings is highlighted in this context.
Article
Chemistry, Organic
Alessandro Cerveri, Mattia Vettori, Andrea Serafino, Giovanni Maestri
Summary: A tBuOK-promoted synthesis of 1,3-dihydro-2H-pyrrol-2-one and 4-methylenepyrrolidin-2-one systems via Conia-ene like intramolecular cyclization is reported. The method demonstrates short reaction times (5 min) and mild reaction conditions (rt), allowing the trapping of a propargyl unit by an amide enolate. An intriguing anionic chain mechanism is involved, facilitating the isomerization of an exo-alkene to yield the otherwise elusive endo-product.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Davide Ruggeri, Elena Motti, Nicola Della Ca', Giovanni Maestri
Summary: The first synthesis of tetrahydropyranes promoted by a silver salt is presented. Cinnamyl ethers undergo a formal dimerization to afford the target heterocycle via sequential C-O bond cleavage/C-H bond functionalization. This cascade reaction allows the assembly of three new bonds and the establishment of up to four stereocenters. The reaction likely proceeds through a cationic manifold that forms the target in a diastereoselective fashion.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Franca Bigi, Daniele Cauzzi, Nicola Della Ca, Max Malacria, Raimondo Maggi, Elena Motti, Yanlan Wang, Giovanni Maestri
Summary: This manuscript provides an overview of the literature on trinuclear complexes with delocalized metal-metal bonds resembling regular aromatics, composed of main group elements. The focus is on the structural and electronic features of stable aromatic clusters, along with their reported catalytic applications, including C-C forming cascades and cross-coupling methods. These examples highlight the unique reactivity exhibited by all-metal aromatic complexes, which often surpass their mononuclear counterparts in terms of chemoselectivity and chemical robustness.
ACS ORGANIC & INORGANIC AU
(2022)
