Article
Chemistry, Inorganic & Nuclear
Kirill K. Geyl, Sergey V. Baykov, Svetlana O. Kasatkina, Polina Yu. Savko, Vadim P. Boyarskiy
Summary: Substituted N-(pyridin-2-yl) ureas or carbamates can act as polynucleophiles and react with palladium(II) bis(isocyanide) complexes to form metallacycles containing azaheterocyclic and urea fragments. Nine new C,N-chelate deprotonated diaminocarbene palladium(II) complexes were synthesized by coupling substituted N-(2-pyridyl)ureas and coordinated isocyanides. This method provides a convenient way for the targeted synthesis of polyfunctional organometallic compounds.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Sabrina Giofre, Camilla Loro, Letizia Molteni, Carlo Castellano, Alessandro Contini, Donatella Nava, Gianluigi Broggini, Egle M. Beccalli
Summary: A useful aminohalogenation reaction for the cyclization of O-alkynyl carbamates under copper catalysis has been developed in this study. N-Halosuccinimides were used as the halogen source, leading to selective intramolecular C-N bond formation and the generation of haloalkylidene substituted heterocycles. The mechanism for the two alternative reaction pathways was investigated by modeling the corresponding transition states at the DFT level.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Sawsan H. Alelaiwi, James R. Mckee
Summary: A direct and effective method for synthesizing primary amine of several polycyclic aromatic compounds through copper (I)-catalyzed Ullmann C-N coupling is reported. This method also allows the synthesis of new N-substituted dibenzothiophene derivatives. The use of inexpensive catalysts and aqueous ammonia as the ammonia source makes this protocol environmentally and economically advantageous.
Article
Chemistry, Applied
Natalia S. Soldatova, Artem V. Semenov, Kirill K. Geyl, Sergey V. Baykov, Anton A. Shetnev, Anna S. Konstantinova, Mikhail M. Korsakov, Mekhman S. Yusubov, Pavel S. Postnikov
Summary: A method for copper-catalyzed N-arylation of diverse oxadiazolones using diaryliodonium salts has been reported with high yields up to 92%. It was found that the steric effects in aryl moieties determined the chemoselectivity of arylations. Mesityl-substituted diaryliodonium salts demonstrated high potential as selective arylation reagents.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Qile Wang, Thomas R. Hoye
Summary: The study presents a novel Cu(I)-catalyzed reaction for introducing different substituents onto benzyne molecules, showing potential for various applications.
Article
Chemistry, Multidisciplinary
Hiroki Tashiro, Masahiro Terada, Itaru Nakamura
Summary: Gold-catalyzed reactions were used to synthesize 2H-azirines with sulfenyl and acyl groups at the 3-position, yielding good to excellent results. These reactions involved internal transfer of sulfinyl oxygen atom and carbene insertion into the N-S bond for ring construction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mohammed B. Alshammari, Ashraf A. Aly, Stefan Braese, Martin Nieger, Lamiaa E. Abd El-Haleem
Summary: Various (thio)ureas, semicarbazides, thiosemicarbazides, thiazolidones, and oxadiazole compounds derived from the [2.2]paracyclophane molecule were successfully synthesized starting with 4-(2.2]paracyclophanyl)isocyanate. The structures of the obtained products were determined using NMR, mass spectrometry, infrared spectroscopy, and high-resolution mass spectrometry (HRMS). X-ray crystallography was used to further confirm the assigned structures.
Article
Chemistry, Multidisciplinary
Yujing Zhang, Xingchao Dai, Jixue Wang, Junxi Liang, Jabor Rabeah, Xia Tian, Xiaoqiang Yao, Yanbin Wang, Shaofeng Pang
Summary: This study introduces an in-situ generated Cu-I catalytic system for the oxidative N-formylation of N-heterocycles with methanol. The formation of N-formamides from acyclic amines is also demonstrated. A possible reaction mechanism and pathway are proposed. The formation of undesired tar-like products is related to the radicals .O-2(-) and .OOH in the catalytic system.
Article
Chemistry, Organic
Bastian L. Springer, Kristina Holzschneider, Fabian Mohr, Stefan F. Kirsch
Summary: A new synthetic route for phenanthro[9,10-d]imidazoles is reported. The target compounds were synthesized through the aminolysis of readily accessible 10,10-diazidophenanthren-9(10H)-one with nucleophilic amines, followed by a self-condensation. X-ray single crystallography was used to determine the molecular structures, and the optical properties of the material were described.
SYNTHESIS-STUTTGART
(2023)
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, Multidisciplinary
Sheuli Sasmal, Gaurav Prakash, Uttam Dutta, Ranjini Laskar, Goutam Kumar Lahiri, Debabrata Maiti
Summary: Site-selective C-H alkynylation of arenes is highly desirable for the synthesis of natural products, drug molecules, and materials. In this study, we developed a Rh(I)-catalyzed protocol for meta-C-H alkynylation, which broadens the scope of this transformation and allows for post-synthetic modifications.
Article
Chemistry, Applied
Hayeon Kwak, Eunsu Kang, Jae Yeong Song, Geunhee Kang, Jung Min Joo
Summary: The development of modular approaches for heteroaromatic cores and substituents is crucial for drug candidates and organic functional materials. A new strategy involving the cyclization of heteroarenes tethered with alkynes through a norbornene bridge was developed. The Pd catalytic system transformed a variety of five-membered heteroarenes to the corresponding benzofused products, demonstrating its versatility in the annulation of (hetero)aromatic rings.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Le-Cheng Wang, Bo Chen, Xiao-Feng Wu
Summary: A novel cobalt-catalyzed carbonylative coupling of ethers with amines has been achieved, leading to the synthesis of biologically active compounds. This protocol presents the first example of direct carbonylative reaction of ethers, providing an important method for the construction of alpha-carbonylated ethers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Changdong Shao, Tianyi Xu, Chen Chen, Qionglin Yang, Chao Tang, Ping Chen, Mingzhu Lu, Zhengsong Hu, Huayou Hu, Tingting Zhang
Summary: A simple and effective method for copper-catalyzed selective C5-H bromination and difluoromethylation of 8-aminoquinoline amides using ethyl bromodifluoroacetate as the bifunctional reagent was developed. The combination of cupric catalyst and alkaline additive enables C5-bromination, while the combination of cuprous catalyst and silver additive enables C5-difluoromethylation. This method exhibits a wide substrate scope and provides easy access to desired C5-functionalized quinolones with high yields.
Article
Chemistry, Multidisciplinary
Yu-Sheng Peng, Wei Wang, Jun Shi, Wei Wu, Jun-Rong Song, Wei-Dong Pan, Ge-Fei Hao, Hai Ren
Summary: In this study, we reported an unprecedented skeletal rearrangement reaction of tetrahydro-beta-carbolines enabled by copper-catalyzed single-electron oxidative oxygenation. The reaction utilized H2O and O-2 as oxygen sources to generate a unique 2-hydroxyl-3-peroxide indoline intermediate, which underwent a multi-step bond cleavage and formation cascade. By using a readily available copper catalyst under open-air conditions, highly important spiro[pyrrolidone-(3,1-benzoxazine)] products were obtained in a single operation. This methodology demonstrated synthetic utility by efficiently synthesizing natural products and the 3-hydroxyl-pyrroloindoline scaffold in only one or two steps.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Camilla Loro, Letizia Molteni, Marta Papis, Egle M. Beccalli, Donatella Nava, Leonardo Lo Presti, Stefano Brenna, Gioele Colombo, Francesca Foschi, Gianluigi Broggini
Summary: A novel synthetic strategy for the direct synthesis of oxazolo-phenoxazine compounds has been achieved through a dimerization/cyclization reaction of 2-benzylamino-phenols. Regioselective formation of 1-benzyl-2-phenyl-6-(aryl-benzyl)amino-benzimidazoles has also been demonstrated using specific starting substrates. The fluorescence emission properties of the synthesized products have been evaluated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Camilla Loro, Julie Oble, Francesca Foschi, Marta Papis, Egle M. Beccalli, Sabrina Giofre, Giovanni Poli, Gianluigi Broggini
Summary: Treatment of O-allyl N-tosyl carbamates with aromatic compounds in the presence of Cu(OTf)(2) or TMSOTf as promoters results in the formation of N-substituted 1-arylpropan-2-amines, 1,2-diarylpropanes, 1,1-diarylpropanes, or indanes, depending on the nature of the promoter and aryl substrates. A proposed mechanism explains the outcome of these C-H based cascades, involving initial acid promoted decarboxylative/deamidative Friedel-Crafts allylation followed by protonation of the allylated arene.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Roberto Sala, Gredy Kiala, Luis F. Veiros, Gianluigi Broggini, Giovanni Poli, Julie Oble
Summary: A method for the directed alkenylation of 2-carboxaldimine-heterocyclopentadienes using Ru3(CO)12 catalyst has been developed. This reaction enables coupling of various electron-poor alkenes with furan, pyrrole, indole, and thiophene 2-carboxaldimines, and does not require additional sacrificial oxidants. Mechanistic insights have been obtained through density functional theory calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Camilla Loro, Letizia Molteni, Marta Papis, Leonardo Lo Presti, Francesca Foschi, Egle M. Beccalli, Gianluigi Broggini
Summary: Treatment of aldehyde-substituted isoxazol-5(4H)-ones with [RuCl2(p-cymene)](2) as the catalyst generates pyrazole-4-carboxylic acids, while treatment of alcohol-substituted isoxazol-5(4H)-ones produces isoxazole-4-carboxylic acids. The presence of intramolecular hydrogen bonding in the substrates plays a crucial role in diverting the reaction towards ring-opening non-decarboxylative pathway.
Article
Chemistry, Organic
Tingting Chen, Jassmin Lahbi, Gianluigi Broggini, Alexandre Pradal, Giovanni Poli
Summary: Two previously unknown protocols for Pd-catalyzed allylic C-H sulfonylation of terminal alkenes have been developed. The former involves a direct Pd(II)-catalyzed oxidative C-H allylic sulfonylation in the presence of sulfinate anions, while the latter includes a sequential one-pot Pd(II)-catalyzed C-H allylic acetoxylation followed by a Pd(0)-catalyzed sulfonylation. The study examined the applicability of both protocols on 25 examples.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Elettra Fasola, Giulia Alboreggia, Stefano Pieraccini, Francesco Oliva, Fatima Ezzahra Agharbaoui, Michela Bollati, Giovanni Bertoni, Sandro Recchia, Marcello Marelli, Umberto Piarulli, Sara Pellegrino, Silvia Gazzola
Summary: This study discovered a novel protein-mimetic peptide that self-assembles into nanofibers in non-polar solvents and forms supramolecular gels in water. This finding provides a promising candidate for future material applications.
FRONTIERS IN CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Samuele Ciceri, Diego Colombo, Enrico M. A. Fassi, Patrizia Ferraboschi, Giovanni Grazioso, Paride Grisenti, Marco Iannone, Carlo Castellano, Fiorella Meneghetti
Summary: Elagolix sodium salt is the first orally active non-peptide gonadotropin-releasing hormone receptor antagonist for the treatment of hormone dependent diseases. A detailed NMR investigation was conducted to analyze the drug and its synthetic intermediates, allowing for the complete assignment of the NMR signals and determination of the stereochemical profile of the atropisomers. These results contribute to the understanding of atropisomerism in drug discovery and can be applied in the design of safer and more effective analogs.
Article
Chemistry, Multidisciplinary
Giovanni Maria Fusi, Tommaso Gandini, Silvia Gazzola, Toni Grell, Valentina Colombo, Luca Pignataro, Umberto Piarulli
Summary: This article reports the synthesis and characterization of chiral (cyclopentadienone)iron complexes (CICs) with different stereochemistry. The complexes were tested in the hydrogenation of ketones and showed good catalytic activity and stereoselectivity imparted by the stereogenic plane.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Camilla Loro, Marta Papis, Francesca Foschi, Gianluigi Broggini, Giovanni Poli, Julie Oble
Summary: A new straightforward approach to synthesizing 1-aryl-2-aminopropanes has been developed using a simple and accessible substrate. This approach involves cascade reactions with arenes and sulfonamide nucleophiles catalyzed by Cu(OTf)(2), resulting in regioselective formation of 1-aryl-2-aminopropanes. The reaction is expected to proceed through a Friedel-Crafts-type allylation of the arene followed by hydroamination.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Marta Papis, Raffaella Bucci, Alessandro Contini, Maria Luisa Gelmi, Leonardo Lo Presti, Giovanni Poli, Gianluigi Broggini, Camilla Loro
Summary: A phosphine-catalyzed domino assembly of six units of 2-bromomethyl acrylates was developed to synthesize polyalkenyl adducts containing two cyclohexenyl rings. This method involves initial dimerization and subsequent trimerization of the substrate, resulting in the formation of seven carbon-carbon bonds and four stereocenters. The protocol has also been successfully scaled up to gram-scale experiments.
Article
Pharmacology & Pharmacy
Marco Zambra, Ivan Randelovic, Francesco Talarico, Adina Borbely, Laura Svajda, Jozsef Tovari, Gabor Mezo, Lizeth Bodero, Sveva Colombo, Federico Arrigoni, Elettra Fasola, Silvia Gazzola, Umberto Piarulli
Summary: Antibody-Drug Conjugates (ADCs) and Small Molecule-Drug Conjugates (SMDCs) are targeted drug-delivery technologies that successfully overcome the side effects of conventional chemotherapy in cancer treatment. By replacing the Val-Ala-p-aminobenzyloxycarbamate linker with the Gly-Pro-Leu-Gly-p-aminobenzyloxycarbamate (GPLG-PABC) sequence, a more potent anti-tumoral effect was achieved in the SMDC, and the released drug was observable after 15 minutes of incubation. These findings have therapeutic significance in developing more efficient and less toxic drug delivery systems.
FRONTIERS IN PHARMACOLOGY
(2023)
Meeting Abstract
Biochemistry & Molecular Biology
Federico Arrigoni, Giulia Antonini, Lizeth Bodero, Francesco Talarico, Monica Civera, Laura Belvisi, Silvia Gazzola, Umberto Piarulli
JOURNAL OF PEPTIDE SCIENCE
(2022)
Meeting Abstract
Biochemistry & Molecular Biology
Silvia Gazzola, Elettra Fasola, Sara Pellegrino, Sandro Recchia, Marcello Marelli, Stefano Pieraccini, Umberto Piarulli
JOURNAL OF PEPTIDE SCIENCE
(2022)
Article
Chemistry, Organic
Marta Papis, Camilla Loro, Michele Penso, Gianluigi Broggini, Francesca Foschi
Summary: The synthesis of modified morpholino monomers was achieved through condensation reactions under Lewis acid conditions, utilizing a simple and efficient method to access diversified optically pure morpholino monomers with high yields and anomeric ratios.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Biotechnology & Applied Microbiology
Gina Ramoni, Carmine Capozzoli, Adriana Bava, Francesca Foschi, Gianluigi Broggini, Fabrizio Beltrametti
Summary: Amycolatopsis coloradensis ATCC 53629 is capable of producing the glycopeptide antibiotic avoparcin as well as a previously undescribed ristosamynil-avoparcin. By selecting a high producer morphological variant within the population and using a new fermentation medium, the productivity of the avoparcin complex was increased. All selected phenotypes, as well as the original population, displayed the ability to produce a complex rich in ristosamynil-avoparcin.
FERMENTATION-BASEL
(2022)
